Compositions of a metal amidine complex and second compound, coating compositions comprising same

ABSTRACT

Described herein are metal amidine complexes in combination with a second compound useful as catalysts in a number of polymerization reactions, including polyurethane and epoxy polymerization reactions. Also described herein are various coating compositions and methods of using same for coating substrates using the metal amidine complexes in combination with a second compound.

This application claims the benefit of U.S. Provisional PatentApplication No. 61/449,709, filed Mar. 6, 2011, incorporated herein byreference in its entirety.

1. FIELD OF THE INVENTION

Described herein are metal amidine complexes in combination with asecond compound that are useful as catalysts for a number ofpolymerization reactions, including polyurethane and epoxypolymerization reactions.

2. BACKGROUND 2.1 Polymerization by Reaction of Epoxy Functional Resinswith Carboxy and Anhydride Functional Compounds, Dicyandiamide andPhenols

Epoxy compounds react with carboxylic acids or with anhydrides. Thisreaction can be catalyzed. Antoon and Koenig (J. Polym. Sci., Polym.Chem. Ed. (1981) 19(2):549-70) studied the mechanism of catalysis bytertiary amines of the reaction of anhydrides with epoxy resins,typically a glycidyl ether of bisphenol A. They pointed out that it isthe quaternary ammonium salt zwitterion that initiated thepolymerization reaction. Matejka and Dusek studied the reaction ofphenylglycidyl ether model compounds with caproic acid in the presenceof a tertiary amine as the catalyst (Polym. Bull. (1986) 15(3):215-21).Based on their experimental data, they suggested that this is anaddition esterification process.

Metal salts and amines have been used as catalysts for theepoxy-carboxyl/anhydride reaction. Whittemore et. al. (U.S. Pat. No.3,639,345) disclosed thermosetting resins using an epoxy functionalbisphenol A and a trimellitic anhydride ester with an amine, animidazole or an aminoalkyl phenol, as the catalyst.

Metal salts or Lewis acid catalysts are also used for theepoxy-carboxyl/anhydride reaction. For example, the catalytic effect ofmetal salts for the epoxy-carboxyl.anhydride reaction was recognized byConnelly et. al. (ZA 6,907,152) who described the use of zinc acetate,chromium acetate, iron octoate, zinc naphthenate, cobalt naphthenate andmanganese naphthenate as catalysts

A major problem with these known catalysts is the poor stability of thecombination of the epoxy and carboxyl/anhydride reactants at ambientroom temperature in the presence of catalyst. The increase in viscosityrequires the epoxy and the carboxyl/anhydride compounds to be formulatedinto two separate packages. A further problem is the yellowing tendencyof amines during the bake or heating cycle.

Additionally, single package epoxy resin systems conventionally includea latent curing agent, typically dicyandiamide. This curing agentrequires a long cure period, even at high temperatures. For example,normally dicyandiamide-epoxy system (e.g., Epon 828, Shell ChemicalCompany), without the presence of an accelerator, requiring curing attemperatures above 180° C. for at least 30 minutes to obtain a curedthermoset for practical applications (adhesives, coatings, andsealants). To increase the curing speed and to reduce the curingtemperature, curing accelerators such as imidazoles and ureas have beenincorporated into epoxy-dicyandiamide systems. The prepared one-packagethermosetting materials, however, suffer from drawbacks, includingproblems with storage stability due, for example, to the basic nature offree imidazoles.

Thus, it is desirable to have a catalyst or catalyst composition, foruse in a single-package epoxy resin system, that does not suffer fromone or more of these drawbacks. Furthermore, it is desirable to havesuch a catalyst or catalyst composition that is capable of curing at anextremely rapid speed and at a reduced cure temperature withoutaffecting the storage stability of the single-package epoxy resinsystem.

2.2 Polyurethane Reactions

The reaction of isocyanates and hydroxyl compounds to form urethanes isthe basis for the production of polyurethanes. Metal compounds (e.g.,tin, zinc and bismuth compounds) and tertiary amines have been known tocatalyze the reaction of isocyanate and hydroxyl groups to formurethane. See Proceedings of Water Borne and High Solids CoatingsSymposium, Feb. 25-27, 1987, New Orleans, at Page 460. Commerciallyavailable catalysts used in this reaction are organotin compounds (e.g.,dibutyltin dilaurate and dibutyltin diacetate), zinc carboxylates,bismuth carboxylates, organomercury compounds and tertiary amines.

There are several problems with these commercially available catalysts.When used in the process for polyurethane coatings, the cure of thecoatings under high humidity or at low temperature conditions is notsatisfactory. They catalyze the undesirable side reaction of isocyanatewith water to form amines and carbon dioxide. The carbon dioxide maycause blisters in the coating and the amines react with isocyanatesresulting in low gloss coatings. Moreover, the cure rate at lowtemperatures is too slow. The commercially available catalysts alsocatalyze the degradation of the resulting polymer product. Furthermore,several of the commercially available urethane catalysts, particularlythose containing heavy metals and tertiary amines, are highly toxic andare environmentally objectionable.

Blocked isocyanates are used in many coating applications, such aspowder coatings, electrocoatings, coil coatings, wire coatings,automotive clear top coatings, stone chip resistant primers, and textilefinishes. Traditionally, these coating processes employ organicsolvents, which may be toxic and/or obnoxious and cause air pollution.In recent years, the legal requirements for low or no pollution of theenvironment have led to an increase in the interest in waterborne andhigh solids coatings. Furthermore, in processes wherein blockedisocyanates are used, heating to an elevated temperature is necessary toremove the blocking group from the blocked isocyanate to form freeisocyanates. A drawback to the use of this process is the hightemperature required to remove the blocking group. The process isextremely slow without a catalyst. It is known that metal compounds suchdialkyltin and certain bismuth and zinc salts are useful catalysts inthese solvent borne coating processes. “Crosslinking withPolyurethanes.” W. J. Blank, ACS Proceedings of Polymeric MaterialsScience and Engineering (1990) 63:931-935.

Conventional bismuth carboxylates, for example, suffer from drawbacksincluding that they do not provide improved resin performance nor arethey effective in water-borne formulations.

For waterborne processes, the catalysts known to be useful areorgano-tin and lead compounds. The toxicity of both lead and tincompounds presents serious environmental hazards. Furthermore, the useof solvents in solvent borne processes further result in the undesirablerelease of toxic and obnoxious chemicals into the environment.

Organotin compounds, such as dibutyltin oxide (DBTO), dioctyltin oxide(DOTO), dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL),dibutyltin diacetate (DBTDA) and the like (reference is made to U.S.Pat. Nos. 4,071,428, 4,615,779 and 4,785,068) are widely used, butsuffer from drawbacks, including poor compatibility with epoxy resinsused in electrocoating, production of films with surface defects such ascissing, and poor hydrolytic stability of these esters leads. They alsosuffer from lack of selectivity towards the polyol isocynate reactionleading to urethane, and can catalyze the degradation of the resultingpolymer product.

2.2.1 Electrocoating Applications

Electrodepositable coatings are widely used, for example, for corrosionprotection for metal substrates, such as those used in the automobileindustry.

The electrodeposition process involves immersing an electroconductivesubstrate into a bath of an aqueous electrocoating composition, thesubstrate serving as a charged electrode in an electrical circuitcomprising the electrode and an oppositely charged counter-electrode.Sufficient electrical current is applied between the electrodes todeposit a substantially continuous, adherent film of the electrocoatingcomposition onto the surface of the electroconductive substrate.

Many cationic electrodeposition compositions used today are based onactive hydrogen-containing resins derived from a polyepoxide and acapped aromatic or aliphatic polyisocyanate curing agent. Capping agentstypically require cure temperatures in excess of 360° F. (182° C.)unless catalysts are used. Metal catalysts, such as stannous salts ormono- or diorganotin compounds, can catalyze the curing or cross-linkingreaction at temperatures in the range 330-365° F. Drawbacks of typicalcatalysts include their cost and adverse environmental impact.

In order to conserve energy, reduce deformation of plastic partsattached to the metal object, and reduce color formation, a lowertemperature cure (compared to catalyst-free or conventional) would bedesirable. For example, the number of effective catalysts available andtheir ability to reduce cure temperatures below 340° F. (171° C.) foraromatic isocyanates, and 380° F. (193° C.) for aliphatic isocyanateswhile maintaining performance properties such as corrosion resistance isseverely limited.

Use of lead compounds also suffers drawbacks because of theenvironmental and toxicological hazards associated with lead compounds.

Tin catalysts suffer drawbacks, for example unsuitability in aqueoussystems and adverse environmental impact. For example, dialkyltin oxidesare subject to a number of regulatory restrictions in various countriesdue to environmental concerns.

Bismuth catalysts also suffer drawbacks. For example, bismuth catalystsare often less effective as catalysts in electocoating applications,compared to, for example, dialkyltin oxides. Furthermore, bismuthcatalysts often suffer from high cost and/or low availability.

2.2.2 Powder Coating Applications

Powder coatings have many potential applications. For example, light andweather resistant coatings may be obtained using heat curable,polyurethane (PUR) powder coatings. The PUR powder coatings currentlycommercially available suffer drawbacks, including the emission ofblocking agents during thermal crosslinking.

One approach to avoiding the emission of blocking agents is to use knownPUR powder coating crosslinking agents containing uretdione groups asdescribed, e.g., in DE-A 2,312,391, DE-A 2,420,475, EP-A 45,994, EP-A45,996, EP-A 45,998, EP-A 639,598 and EP-A 669,353. Uretdione powdercoating crosslinking agents suffer from drawbacks, including therelatively low reactivity of the internally blocked isocyanate groups,which generally require stoving temperatures of at least 160° C.Furthermore, curing at temperatures as low as 100° C. suffers fromdrawbacks, including that the reaction is impracticably slow.

Efforts to solve this problem through the use of various catalysts—suchas tin(II) acetate, tin(II) octoate, tin(II) ethylcaproate, tin(II)laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate(for example EP 803 524, EP-A 45,994, EP-A 45,998, EP-A 601,079, WO91/07452 or DE-A 2,420,475), iron(III) chloride, zinc chloride, zinc2-ethylcaproate and molybdenum glycolate or tertiary amines such astriethylamine, pyridine, methylpyridine, benzyldimethylamine,N,N-endoethylenepiperazine, N-methylpiperidine,pentamethyldiethylenetriamine, N,N-dimethylaminocyclohexane andN,N′-dimethylpiperazine (for example EP-A 639 598),N,N,N′-trisubstituted amidines (U.S. Pat. No. 5,847,044), tetra alkylammonium compounds and combinations with reactive compounds that areable to react with acid groups, (E. Spyrou, H. Loesch, and J. V. Weiβ,“Highly Reactive, Blocking Agent-Free Polyurethane Powder Coatings”, 8thNuernberg Congress, Creative Advances in Coatings Technology; Nuernberg,Germany, April, 2005, U.S. Pat. No. 6,914,115 B2), metalloorganiccarboxylate, alcoholate, or acetylacetonate, and combinations of thesecatalysts with reactive agents such as an epoxy, or an oxazolinecompound (WO 00/34355, U.S. Pat. No. 7,019,088 B1)—suffer additionaldrawbacks, including, for example, low catalytic efficiency, sensitivityto the presence of water, and catalysis of degradation of polyurethaneproduct, and cure temperature.

Thus, an objective of the disclosure is to develop catalysts with highcatalytic efficiency for the isocyanate-hydroxyl reaction to formurethane and/or polyurethane. Another objective of the disclosure is todevelop catalysts which provide improved cure at a lower temperature andis less sensitive to the presence of water. Yet another objective of thedisclosure is to provide catalysts for the isocyanate-hydroxyl reactionwhich would not catalyze the undesired side reaction of water withisocyanates or the undesired degradation of the polyurethane. It isdesirable to have a catalyst or catalyst composition that does notexhibit these side effects or suffer from one or more of thesedrawbacks.

3. SUMMARY

Described herein, in one aspect, are compositions comprising a metalamidine complex and one or more second compounds. Also described hereinare the use of such compositions for the reaction of compounds withisocyanate and hydroxyl functional groups to form urethane and/orpolyurethane, and processes employing such catalyst compositions. Incertain embodiments, a composition comprising a metal amidine complexand one or more second compounds exhibits a synergistic effect, forexample in the production of urethanes and polyurethanes which areimportant in many industrial applications, such as: coatings, foams,adhesives, sealants, and reaction injection molding (RIM) plastics. Incertain embodiments, the compositions described herein aresynergistically effective in catalyzing both a solvent borne and awaterborne process to form such coatings.

Described herein are also methods of catalyzing the process forde-blocking blocked isocyanates—e.g., ketoxime, pyrazole, alcohol,glycol or phenol blocked products—to form crosslinked coatings. Moreparticularly, the present disclosure relates, in one aspect, to the useof a composition comprising a metal amidine compleox and one or moresecond compounds effective in catalyzing both a solvent borne and awaterborne process to form such crosslinked coatings. Thus, providedherein is a method comprising catalyzing catalyzing both a solvent borneand a waterborne process to form such crosslinked coatings using thesecompositions. These compositions also can be utilized as part of amethod comprising catalyzing blocked isocyanates in cationicelectrocoating applications. In another aspect, provided herein is ablocked isocyanate group-containing electrocoating compositioncomprising a composition comprising a metal amidine comples and one ormore second compounds, having low-temperature curability and corrosionresistance. The compositions provided herein can exhibit such desirableproperties as, for example, reduced cure temperatures, improvedultrafiltration, reduced grind preparation, increased deposition rate,improved dispersability or emulsifiability, reduced toxicity, easierhandling, and improved color maintenance.

In one aspect, the present disclosure is directed to compositionscomprising a metal amidine complex and one or more second compoundswhich effectively catalyze the reaction of epoxy-carboxyl/anhydride atlower temperatures, as compared to, for example, conventional catalysts.The use of these catalyst compositions in the coating process not onlyreduces yellowing, but also provides excellent room temperaturestability and excellent humidity resistance. The improved stability withthe use of the catalysts of this disclosure provides for the formulationof a single packaged product. Thus, in certain embodiments is provided asingle packaged product comprising such a composition, as well as anepoxy compound and a carboxyl/anhydride compound, as describedhereinbelow.

In one embodiment, the metal amidine complexes described herein comprisea metal, an amidine, and a carboxylate. In certain embodiments, themetal amidine carboxylate complexes are metal(II) amidine carboxylatecomplexes. In a particular embodiment, the metal amidine complex is ofthe chemical formula M(amidine)_(w)(carboxylate)₂, where w is an integerfrom 1 to 4, for example 2 or 4. In certain embodiments, the metal iszinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth,cadmium, aluminum, zirconium, tin, hafnium, titanium, lanthanum,vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.In a particular embodiment, the metal is zinc. In a particularembodiment, the metal is in the +2 oxidation state.

In certain embodiments, the amidine of the metal amidine complex is anamidine of formulae I-VIII

wherein R¹ is hydrogen, an organic group attached through a carbon atom(such as C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl), an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms;

-   R² and R³ are each independently hydrogen or an organic group    attached through a carbon atom (such as C₁-C₂₅ alkyl, C₂-C₂₅ alkyl    interrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl    which is unsubstituted or substituted by C₁-C₄ alkyl and/or    carboxyl; C₅-C₁₅ cycloalkenyl which is unsubstituted or substituted    by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉    phenylalkyl which is unsubstituted or substituted on the phenyl ring    by C₁-C₄ alkyl), or are joined to one another by an N═C—N linkage to    form a heterocyclic ring with one or more hetero atoms or a fused    bicyclic ring with one or more heteroatoms;-   R⁴ is hydrogen, an organic group attached through a carbon atom    (such as C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted by oxygen or sulfur;    C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted or    substituted by C₁-C₄ alkyl and/or carboxyl; C₅-C₁₅ cycloalkenyl    which is unsubstituted or substituted by C₁-C₄ alkyl and/or    carboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which is    unsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl) or a    hydroxyl group which can be optionally etherified with a hydrocarbyl    group having up to 8 carbon atoms;-   R⁵, R⁶, R⁷, and R⁸ are independently hydrogen, alkyl, substituted    alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics,    ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitro    groups, keto groups, ester groups, or carbonamide groups optionally    alkyl substituted with alkyl, substituted alkyl, hydroxyalkyl, aryl,    aralkyl, cycloalkyl, heterocycles, ether, thioether, halogen,    —N(R)₂, polyethylene polyamines, nitro groups, keto groups or ester    groups;-   R⁹, R¹⁰ and R¹¹ are independently hydrogen, alkyl, alkenyl or alkoxy    of 1 to 36 carbons, cycloalkyl of 6 to 32 carbons, alkylamino of 1    to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl,    hydroxyalkyl, hydroxycycloalkyl of 1 to 20 carbon atoms,    methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbon atoms    (wherein the aryl group of the aralkyl is further substituted by    alkyl of 1 to 36 carbon atoms, ether, thioether, halogen, —N(R)₂,    polyethylene polyamines, nitro groups, keto groups, ester groups, or    carbonamide groups) (wherein the alkyl group of the aralkyl is    optionally substituted with alkyl, substituted alkyl, hydroxyalkyl,    aryl, aralkyl, cycloalkyl, heterocyclics, ether, thioether, halogen,    —N(R)₂, polyethylene polyamines, nitro groups, keto groups or ester    groups), wherein the R of —N(R)₂ is alkyl, alkylene, aryl, aralkyl,    cycloalkyl or heterocyclic radical, optionally substituted with    halogen, nitro, alkyl, alkoxy or amino, and, when m=1, R is hydrogen    or a plurality of radicals optionally joined by hetero atoms O, N or    S;-   m=1 or 2; n=2 or 3;

wherein each of R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ is hydrogen, (cyclo)alkyl,aryl, aromatic, organometallic, a polymeric structure, or together canform a cycloalkyl, aryl, or an aromatic structure, and wherein R₂₁, R₂₂,R₂₃, R₂₄, and R₂₅ can be the same or different. As used herein,“(cyclo)alkyl” refers to both alkyl and cycloalkyl. When any of the Rgroups “together can form a (cyclo)alkyl, aryl, and/or aromatic group”it is meant that any two adjacent R groups are connected to form acyclic moiety, such as the rings in structures (V)-(VIII) below.

It will be appreciated that in some embodiments, the double bond betweenthe carbon atom and the nitrogen atom that is depicted in structure (IV)may be located between the carbon atom and another nitrogen atom ofstructure (IV). Accordingly, the various substituents of structure (IV)may be attached to different nitrogens depending on where the doublebond is located within the structure.

In certain embodiments, the cyclic guanidine comprises the guanidine ofstructure (IV) wherein two or more R groups of structure (IV) togetherform one or more rings. In other words, in some embodiments the cyclicguanidine comprises ≧1 ring. For example, the cyclic guanidine caneither be a monocyclic guanidine (1 ring) as depicted in structures (V)and/or (VI) below, or the cyclic guanidine can be polycyclic (≧2 rings)as depicted in structures (VII) and (VIII) above.

Each substituent of structures (V) and/or (VI), R₂₁-R₂₇, can comprisehydrogen, (cyclo)alkyl, aryl, aromatic, ogranometallic, a polymericstructure, or together can form a cycloalkyl, aryl, or an aromaticstructure, and wherein R₂₁-R₂₇ can be the same or different. Similarly,each substituent of structures (VII) and (VIII), R₂₁-R₂₉, can behydrogen, alkyl, aryl, aromatic, organometallic, a polymeric structure,or together can form a cycloalkyl, aryl, or an aromatic structure, andwherein R₂₁-R₂₉ can be the same or different. Moreover, in someembodiments of structures (V) and/or (VI), certain combinations ofR₂₁-R₂₇ may be part of the same ring structure. For example, R₂₁ and R₂₇of structure (V) may form part of a single ring structure. Moreover, insome embodiments, it will be understood that any combination ofsubstituents (R₂₁-R₂₇ of structures (V) and/or (VI) as well as R₂₁-R₂₉of structures (VII) and/or (VIII) can be chosen so long as thesubstituents do not substantially interfere with the catalytic activityof the cyclic guandine.

In certain embodiments, each ring in the cyclic guanidine is comprisedof ≧5-members. For instance, the cyclic guanidine may be a 5-memberring, a 6-member ring, or a 7-member ring. As used herein, the term“member” refers to an atom located in a ring structure. Accordingly, a5-member ring will have 5 atoms in the ring structure (“a” and/or “b”=1in structures (V)-(VIII)), a 6-member ring will have 6 atoms in the ringstructure (“a” and/or “b”=2 in structures (V)-(VIII)), and a 7-memberring will have 7 atoms in the ring structure (“a” and/or “b”=3 instructures (V)-(VIII)) It will be appreciated that if the cyclicguanidine is comprised of ≧2 rings (e.g., structures (VII) and (VIII),the number of members in each ring of the cyclic guanidine can either bethe same or different. For example, one ring may be a five-member ringwhile the other ring may be a six-member ring. If the cyclic guanidineis comprised of ≧3 rings, then in addition to the combinations cited inthe preceding sentence, the number of members in a first ring of thecyclic guanidine can be different from the number of members in anyother ring of the cyclic guanidine.

It will also be understood that in certain embodiments of the cyclicguanidine the nitrogen atoms of structures (V)-(VIII) can further haveadditional atoms attached thereto. Moreover, in some embodiments, thecyclic guanidine can either be substituted or unsubstituted. Forexample, as used herein in conjunction with the cyclic guanidine,“substituted”, in certain embodiments, refers to a cyclic guanidinewherein R₂₅, R₂₆, and/or R₂₇ of structures (V) and/or (VI) and/or R₂₉ ofstructures (VII) and/or (VIII) is not hydrogen. As used herein inconjunction with the cyclic guanidine, “unsubstituted”, in certainembodiments, refers to a cyclic guanidine wherein R₂₁-R₂₇ of structures(V) and/or (VI) and/or R₂₁-R₂₉ of structures (VII) and/or (VIII) ishydrogen. In some embodiments, the substituted cyclic guanidine is1,5,7-triazabicyclo[4.4.0]dec-5-ene.

In certain embodiments, the amidine of the metal amidine complex is notan amidine of Formulae (I)-(III).

In certain embodiments, the carboxylate of the metal amidine complex isthe carboxylate of a carboxylic acid of the following formula:

wherein R₁₁ is hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₁₆,a 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or6-membered heterocyclic ring which is benzo-fused and is unsubstitutedor substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; or aradical of one of the following formulae:

wherein R₁₂, R₁₃, R₁₄ and R₁₅ independently are hydrogen, hydroxyl,C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; or are —COR₆, with the proviso that, if one of the radicalsR₁₂, R₁₃, R₁₄ and R₁₅ is hydroxyl, the other radical attached to thesame carbon atom is other than hydroxyl; or else R₁₂ and R₁₃ or R₁₄ andR₁₅, together with the carbon atom to which they are attached, form anunsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ring;wherein R₁₆ is hydroxyl, C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which isinterrupted by oxygen or sulfur; or

wherein R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ are independently hydrogen, hydroxyl,halogen, nitro, cyano, CF₃, —COR₆, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈ alkoxy, C₂-C₁₈alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈ alkylthio,C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; phenoxy or naphthoxy which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkoxy which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkoxy which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or else the radicals R₃₈ and R₃₉ or the radicals R₃₉ and R₄₀ or theradicals R₄₀ and R₄₁ or the radicals R₃₇ and R₄₁, together with thecarbon atoms to which they are attached, form an unsubstituted or C₁-C₄alkyl-, halogen- or C₁-C₄ alkoxy-substituted benzo ring, with theproviso that at least one of the radicals R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ ishydrogen;

-   R₄₂ is hydroxyl, halogen, nitro, cyano, CF₃, C₁-C₂₅ alkyl, C₂-C₂₅    alkyl which is interrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl,    C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxgyen or    sulfur; C₁-C₁₈ alkylthio or C₂-C₂₄ alkenyl;-   R₄₃ and R₄₄ are independently hydrogen, C₁-C₂₅ alkyl, C₁-C₁₈ alkoxy    or —Y—(CH₂)_(s) COR₆;-   R₄₅ and R₄₆ are independently hydrogen, C₁-C₂₅ alkyl, C₃-C₂₅ alkyl    which is interrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₅-C₁₅    cycloalkyl which is unsubstituted or substituted by C₁-C₄ alkyl;    phenyl or naphthyl which is unsubstituted or substituted by C₁-C₄    alkyl;-   X₁₁ is a direct bond, oxygen, sulfur, C(O), C₁-C₁₈ alkylene, C₂-C₁₈    alkylene which is interrupted by oxygen or sulfur; C₂-C₁₈    alkenylene, C₂-C₁₈ alkynylene, C₂-C₂₀ alkylidene, C₇-C₂₀    phenylalkylidene or C₅-C₈ cycloalkylene, with the proviso that, if m    and n are 0, X₁₁ is other than oxygen and sulfur;-   Y is oxygen or

-   R_(a) is hydrogen or C₁-C₈ alkyl;-   e and f independently of one another are integers from 0 to 10, p is    an integer from 0 to 4, and s is an integer from 1 to 8. In certain    embodiments, the carboxylate of the metal amidine complex is    formate, acetate, 2-ethylhexanoate, or neodecanoate.

In certain embodiments, the metal amidine complex is one as described inU.S. Pat. No. 7,485,729 to Hsieh et al, herein incorporated by referencein its entirety. Procedures for preparing the metal amidine complexesdescribed herein can be found at cols. 21-22 and Table 2 of U.S. Pat.No. 7,485,729, specifically incorporated herein by reference.

In certain embodiments, the second compound of the compositioncomprising a metal amidine complex and one or more second compounds is ametal compound, a tertiary amine, or an acid.

In certain embodiments, the metal of the metal compound is tin (e.g.,stannous), mercury, bismuth, barium, zinc, calcium, cadmium, zirconium,aluminum, nickel, manganese, vanadium, iron, cerium, thorium, cobalt,copper, titanium, hafnium, lithium, lead, or potassium. In particularembodiments, the metal of the metal compound is zinc or bismuth. Incertain embodiments, the metal is a metal carboxylate. In certainembodiments, the carboxylate of the metal carboxylate is a carboxylte asdescribed in paragraph [0037], above. In a specific embodiment, thesecond compound is zinc acetylacetonate (acac).

In certain embodiments, the tertiary amine is an imidazole, amorpholine, an ethylenediamine, or a trialkylamine. In a particularembodiment, the tertiary amine is an imidazole.

In certain embodiments, the acid is a carboxylic acid, a sulfonic acid,a phosphoric acid, or a phosphate. In certain embodiments, the acid isan aliphatic carboxylic acid, such as isononanoic acid.

In various specific embodiments, the second compound is one of thecompounds set forth in the following tables:

Metal Compound Tin Dibutyltin dilaurate Dibutyltindiacetate Dibutyltindimercaptide Dibutyltin biisooctylmaleate Dialkyltin dialkylmercaptoacid Dibutyltin di-2-ethylhexanoate Dibutyltin dimaleate Dibutyltindiisooctylmercapto acetate Dimethyltin dimaleate Dimethyltindimercaptide Dimethyltin diisooctylmercapto-acetate Dioctyltin dilaurateDimethyltin dilaurate Dioctyltin diisooctylmercapto-acetate Dioctyltindimercaptide Dioctyltin dilaurate Dibutyltin oxideMonobutyltindihydroxychloride Dioctyltin dineodecanoate Organotinhalides Dibutyltin S,S-Dibutyldithiocarbonate DibutyltinBis-O-Phenylphenate Dibutyltin Maleate Dimethyltin Dichloride StannousOctoate Oxalate Stearate Naphthenate Mercury Phenylmercuric acetatePhenylmercuric propionate Bismuth Octoate Neodacanoate NaphthenateStearate Triphenylbismuth Barium Nitrate Zinc Octoate Neodecanoateacetylacetonate Oxalate, naphthenate, alkyl sulfonate, aryl sulfonate,organophosphates Calcium Naphthenate, octoate, neodecanoate,alkylsulfonate, aryl sulfonate Cadmium Octoate Zirconium acetylacetonate6-methylheptanedione Aluminum Dionate Nickel Acetylacetonate ManganeseNaphthenate Vanadium Acetylacetonate Iron Fe III acetylacetonate CeriumNaphthenate, octoate, neodecanoate, alkylsulfonate, aryl sulfonateThorium acac Cobalt Octoate Dionate Copper Acac Titanium Tetrabutoxide,octoate, Neodecanoate, Oleate, Alkoxides, alkylsulfonate, aryl sulfonateHafnium diketonate Lithium Neodecanoate Acetate Lead StannateAcetylacetonate Dioxide Potassium Octoate Acetate

Tertiary amines Bis-(2-dimethylaminoethyl) etherBis-(2-diethylaminoethyl) ether N,N-DimethylcyclohexylamineN,N,N′,N′,N″-Pentamethyldiethylenetriamine TriethylenediamineN-Ethylmorpholine N-Cocomorpholine N,N-DimethylpiperazineN-Methylimidazole N-(3-Aminopropyl)imidazole 1,2-DimethylimidazoleBis(dimethylaminoethyl)ether N,N,N′,N′-TetramethylhexanediamineN,N′,N′-TrimethylaminoethylpiperazineN,N,N′,N′-Tetramethylethylenediamine N-Methyl-N′-hydroxyethylpiperazineN,N′,N′-Trimethylaminoethylethanolamine 2,2′-DimorpholinodiethyletherN,N-Dimethylhexadecylamine 4-[2-(Dimethylamino)ethyl]morpholine N-ethylmorpholine N-methyl morpholine N-butyl morpholine N-methoxyethylmorpholine N,N,N′,N′,N″-PentamethyldipropylenetriamineDimethylaminoethoxyethanol Dimethylethanolamine1,3,5-Tris[3-(Dimethylamino)propyl]hexahydro-s-triazine2-Hydroxypropyltrimethylammonium formate 2,4,6-Tris(dimethylaminomethyl)phenol 1,4-diazabicyclo[2.2.2]octane (DABCO)1,8-Diazabicyclo[5,4,0]undec-7-ene2-Methyl-1,4-diaza[2.2.2]-bicyclo-octane N,N′-dimethylaminoethylN,methyl ethanolamine Triethylamine N-hydroxy-alkyl quaternary ammoniumcarboxylate Dimethylcyclohexylamine DimethyldodecylamineN,N,N′,N′-Tetramethyl-1-3-butane diamine Pentamethyl-diethylene triamineN,N,N′,N′-Tetramethyl-n-hexyl diamine N,N-dimethyl cyclohexylamineTris(dimethylaminopropyl)amine N-methyl dicyclohexylamineBis(N,N-dimethyl-3-amino-propyl)amine Quinuclidine(1,4-ethylenepiperdine) 2-methylaminoethyl-1,3-dimethylaminopropyl etherN,N-dimethyl-N′,N′-2-hydroxy(propyl)-1,3-propylene diamineN,N,N′-trimethyl-N′hydroxyethyl-bis(amino ethyl)etherN,N-bis(3-dimethylamino-propyl)amino-2-propanol(N,N-dimethylaminoethoxy) ethanol N,N′-dimorpholinodiethyl ether

Acids Dodecylbenzene Sulfonic Acid Dinonyl naphthalene sulfonic acidDinonyl naphthalene disulfonic acid Phenyl Acid Phosphate IsoOctyl AcidPhosphate Isononanoic Acid

In various specific embodiments, the metal amidine comples and secondcompound can be: Zn(1-methylimidazole)₂(acetate)₂ and DABCO;Zn(1-methylimidazole)₂(acetate)₂ and zinc acetylacetonate;Zn(1-methylimidazole)₂(acetate)₂ and dibutyltin dilaurate;Zn(1-methylimidazole)₂(acetate)₂ and zirconium acetylacetonate;Zn(1-Methylimidazole)₂(2-Ethylhexanoate)₂ and a bismuth carboxylate;Zn(1,1,3,3-Tetramethylguanidine)₂(2-Ethylhexanoate)₂ and a bismuthcarboxylate; Zn(1-methylimidazole)₂(acetate)₂ and a bismuth carboxylate;Zn(1-methylimidazole)₂(acetate)₂ and lithium neodecanoate;Zn(2-Ethylhexanoate)₂(acetate)₂ and phenylmercuric acetate;Zn(1-methylimidazole)₂(acetate)₂ and dinonylnaphthalene disulfonate;Zn(1-methylimidazole)₂(acetate)₂ and 1,2-dimethylimidazole; orZn(1-methylimidazole)₂(acetate)₂ and 2-methylimidazole.

In a particular embodiment is provided a powder coating compositioncomprising a catalyst composition comprising a metal amidine comples andzinc acetylacetonate.

In certain embodiments, the composition comprises a metal amidinecomplex and a second compound, wherein the second compound is present inan amount from between about 10% and about 80% of the composition byweight, or from about 20% to about 70%, or from about 30% to about 60%,or from about 40% to about 50%.

In certain embodiments, the second agent is not a zinc carboxylate or abismuth carboxylate

Provided herein are also powder coatings, and liquid coatings such ascoil coating, can coating, wire coating, plastic coatings, eachcomprising as a catalyst the metal amidine complex described herein. Inone embodiment is provided a polyurethane powder coating compositioncontaining A) a binder component which is solid below 40° C. and liquidabove 130° C. and has an OH number of about 25 to about 200 and a numberaverage molecular weight of about 400 to about 10,000; B) a polyadditioncompound which is solid below 40° C. and liquid above 125° C. andcontains uretdione groups and optionally free isocyanate groups and isprepared from aliphatic and/or cycloaliphatic diisocyanates and/oraromatic isocyanates; and C) one or more cataylst compositionscomprising a metal amidine complex and one or more second compounds, asdescribed herein. In certain embodiments, components A) and B) arepresent in amounts such that component B) has about 0.6 to about 1.4isocyanate groups for each hydroxyl group present in component A) andthe amount of component C) is about 0.05 to about 10 wt. %, based on thetotal weight of the coating composition. In certain embodiments, thepolyurethane powder coating further comprises D) an acid scavenger, forexample to react with the free carboxyl groups in the binder. In certainembodiments, the polyurethane powder coating is useful for preparingand/or used in coating heat resistant substrates. Thus, in certainembodiments is provided a method comprising coating a substrate with apolyurethane powder coating composition described above, and curing saidcoated substrate.

In certain embodiment is provided a coating composition comprising acarboxyl- and/or anhydride-functional compound, a dicyandiamide, and/orphenols, further comprising one or more cataylst compositions comprisinga metal amidine complex and one or more second compounds, as describedherein. The use of such a catalyst composition in the epoxy-carboxylanhydride reaction improves the stability of the reactants at roomtemperature and avoids yellowing or blistering in the coating produced.Furthermore, the improved stability of the reactants in the presence ofthe catalyst enables a single packaged product for theepoxy-carboxy/ahydride mixture.

Provided herein are also polyurethane powder coating compositionscomprising one or more cataylst compositions comprising a metal amidinecomplex and one or more second compounds, as described herein. Incertain embodiments, the polyurethane powder coating compositions do notrelease reaction products, have increased reactivity and yieldcompletely crosslinked coatings at distinctly lower stoving temperaturesor at correspondingly shorter stoving times than previously known priorart powder coating compositions containing uretdione curing agents,without yellowing of the formulation. Without being limited bymechanism, it is believed that the metal amidine complex catalystsdescribed herein so strongly accelerate the dissociation of uretdionegroups that polyurethane powder coating compositions may be formulatedwith them using known uretdione curing agents such that the powdercoating compositions crosslink to yield high quality coatings atrelatively low stoving temperatures and within a short time, with noyellowing.

In certain embodiments, provided herein are uretdione-containing coatingcompositions comprising a) a binder having hydroxyl groups, b) apolyaddition compound having uretdione groups and optionally freeisocyanate groups as a hardener, c) one or more cataylst compositionscomprising a metal amidine complex and one or more second compounds, asdescribed herein, and optionally d) auxiliary agents and additives. Incertain embodiments, the binder is free of carboxyl groups or theconcentration of carboxyl groups is less than the concentration ofcatalyst composition (c) or, in the case of a higher concentration ofcarboxyl groups compared to the concentration of the catalyst (c) used,an amount of an acid scavenger (such as, for example, epoxies,carbodiimides, trialkylorthoformates, amine compounds, or oxazolines) isadded that is necessary for blocking the amount of carboxyl groups forachieving the required concentration of the catalyst (c). In certainembodiments, such uretdione-containing coating compositions are curableat lower temperatures as compared to those without any catalyst (c), orwith conventional catalysts alone such as free amidines.

In certain embodiments, provided herein is a coating compositioncomprising an organic binder (for example, a film-forming binder, suchas a coating material), and, as corrosion inhibitors, one or morecatalyst composition comprising a metal amidine complex and one or moresecond compounds, as described herein. In such embodiments, the catalystcompositions are used in coating compositions for protecting metallicsurfaces. Also provided are methods of inhibiting the corrosion of asubstrate, comprising application a coating composition as described inthis paragraph, and curing the coated substrate.

In certain embodiments provided herein is a coating compositioncomprising a silane terminated polymer, and a metal amidine complexdescribed herein, or a catalyst composition comprising a metal amidinecomplex and one or more second compounds, as described herein.

4. DETAILED DESCRIPTION 4.1 Metal Amidine Complexes

In accordance with the present disclosure is provided a compositioncomprising a metal amidine complex and one or more second compounds (asdescribed herein) for use in, for example, polyurethane and epoxycoatings. The catalyst compositions are suitable for powder,solventborne, solventless and waterborne coatings.

In certain embodiments, the amidine of the metal amidine complex has theformula

wherein R¹ is hydrogen, alkyl of 1 to 25 carbon atoms, an amine groupwhich can be substituted, for example by an optionally substitutedhydrocarbyl group, or a hydroxyl group which can be etherified, forexample with an optionally substituted hydrocarbyl group having up to 8carbon atoms; R² and R³ each independently represent hydrogen or anorganic group attached through a carbon atom or are joined to oneanother to form (with the linking —N═C—N—) a heterocyclic ring, with oneor more hetero atoms or a fused bicyclic ring with one or moreheteroatoms, and R⁴ represents hydrogen, an organic group attachedthrough a carbon atom or a hydroxy group which can be etherified, forexample with an optionally substituted hydrocarbyl group having up to 8carbon atoms. When R¹ or R⁴ is an organic group it can for examplecontain 1 to 40 carbon atoms or can be a polymeric group, for examplehaving a molecular weight of 500 to 50,000. The groups R¹, R², R³, R⁴could contain as substituents a total of at least two or more alcoholichydroxyl groups.

In certain embodiments, the amidine of the metal amidine complex is notan amidine of the aforementioned formula.

In certain embodiments, the amidine of the metal amidine complex isN′-cyclohexyl-N,N-dimethylformamidine,N′-methyl-N,N-di-n-butylacetamidine,N′-octadecyl-N,N-dimethylformamidine,N′-cyclohexyl-N,N-dimethylvaleramidine,1-methyl-2-cyclohexyliminopyrrolidine,3-butyl-3,4,5,6-tetrahydropyrimidine,N-(hexyliminomethyl)morpholine,N-(α-(decyliminoethyl)ethyl)pyrrolidine,N′-decyl-N,N-dimethylformamidine,N′-dodecyl-N,N-dimethylformamidine, N′-cyclohexyl-N,N-acetamidine,pentamethylguanidine, tetramethylguanidine, or heptamethylisobiguanide

In certain embodiments, the amidine of the metal amidine complex is anamidine in which one of the pairs R²-R³ or R²-R⁴ forms a 5 to 7 memberedring consisting of the two amidine nitrogen atoms and one of the pairsR¹-R³ or R¹-R⁴ forms a 5 to 9 membered ring consisting of one amidinenitrogen atom and carbon atoms. In specific embodiments, the amidine is1,5-diazabicyclo(4.3.0) none-5-ene, 1,8-diazabicyclo(5.4.0) undec-7-ene,1,4-diazabicyclo(3.3.0) oct-4-ene, 2-methyl-1,5-diazabicyclo(4.3.0)none-5-ene, 2,7,8-trimethyl-1,5-diazabicyclo(4.3.0) none-5-ene,2-butyl-1,5-diazabicyclo(4.3.0) none-5-ene or 1,9-diazabicyclo(6.5.0)tridec-8-ene.

Particular catalytic amidine groups are those in which the groups R² andR³ are joined to form (with the linking —N═C—N—) a heterocyclic ring,for example an imidazoline, imidazole, tetrahydropyrimidine,dihydropyrimidine or pyrimidine ring. Acyclic amidines and guanidinescan alternatively be used.

In other embodiments, the amidine of the metal amidine complex is anamidine of the following formula:

where R⁵, R⁶, R⁷, and R⁸ are independently represent hydrogen, alkyl, orsubstituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,heterocyclics, ether, thioether, halogen, —N(R)₂, polyethylenepolyamines, nitro groups, keto groups, ester groups, or carbonamidegroups, alkyl substituted with the various functional groups describedabove. In other embodiments, the amidine of the metal amidine complex isnot an amidine of the aforementioned formula.

In certain embodiments, the amidine of the metal amidine complex isN-(2-Hydroxyethyl)imidazole, N-(3-Aminopropyl)imidazole,4-(hydroxymethyl) Imidazole, 1-(tert-butoxycarbonyl)imidazole,Imidazole-4-propionic acid, 4-carboxylmidazole, 1-butylimidazole,2-methyl-4-imidazolecarboxylic acid, 4-formyl imidazole,1-(ethoxycarbonyl)imidazole, reaction product of propylene oxide withimidazole and 2-methyl imidazole, 1-trimethylsilyl imidazole,4-(hydroxymethyl) Imidazole hydrochloride, copolymer of1-chloro-2,3-epoxypropane and imidazole, 1(p-toluenesulfonyl)imidazole,1,1′-carbonylbisimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole,2-phenyl-2-imidazoline pyromellitate, 4-(hydroxymethyl) Imidazolepicrate, reaction product of 2-propenoic acid with4,5-dihydro-2-nonyl-1H-imidazole-1-ethanol and2-heptyl-4,5-dihydro-1H-imidazole-1-ethanol, disodium salts,1-(cyanoethyl)-2-undecylimidazole trimellitate,1-(2-hydroxypropyl)imidazole formate, sodium imidazolate, or silverimidazolate.

In certain embodiments, the amidine of the metal amidine complesx is acyclic amidine imidazoline or tetrahydropyrimidine of the formula:

in which n=2 or 3, m=1 or 2, R⁹, R¹⁶ and R¹¹ are identical or different,and represent hydrogen, alkyl, or substituted alkyl, hydroxyalkyl, aryl,aralkyl, cycloalkyl, heterocyclics, ether, thioether, halogen,—N(R)₂,polyethylene polyamines, nitro groups, keto groups, ester groups,or carbonamide groups, alkyl substituted with the various functionalgroups described above, and R represents alkyl, alkylene, an aryl,aralkyl, cycloalkyl or heterocyclic radical, substituted if desired withhalogen, nitro groups, alkyl groups, alkoxy groups or amino groups, and,when m=1, represents also hydrogen, a plurality of radicals being ableto be joined, also by hetero atoms such as O, N or S, if desired. Saltsof the above structures include carboxylic (aliphatic, aromatic and polycarboxylic), carbonic, sulfonic and phosphoric acid salts. In certainembodiments, the amidine of the metal amidine complex is not an amidineof the aforementioned formula.

In other embodiments, R⁹, R¹⁰, R¹¹ are independently hydrogen, alkyl,alkenyl or alkoxy of 1 to 36 carbons, cycloalkyl of 6 to 32 carbons oralkylamino of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenyl, hydroxyalkyl or hydroxycycloalkyl of 1 to 20 carbon atoms,methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbon atoms,said aralkyl wherein the aryl group is further substituted by alkyl of 1to 36 carbon atoms.

When m=2, R is alkylene of 1 to 12 carbons or arylene of 6 to 10carbons, or a plurality of radicals being able to be joined, containinghetero atoms also by hetero atoms such as O, N or S, if desired.

In some embodiments imidazoline structures are where R is a long chainalkyl up to 18 carbon atoms, m=1 and R¹¹ is one of 2-hydroxyethyl, or2-aminoethyl or 2-amido ethyl substituents.

In certain embodiments, the amidine of the metal amidine complex is1H-Imidazole-1-ethanol, 2-(8Z)-8-heptadecenyl-4,5-dihydro,1H-Imidazole-1-ethanol, 2-(8Z)-8-heptadecenyl-4,5-dihydro, monoacetatesalt, 1H-Imidazole-1-ethanol, -4,5-dihydro,-2-(9Z)-9-octadecenyl,1H-Imidazole, 4,5-dihydro,-2-(9Z)-9-octadecenyl, oleyl hydroxyethylimidazoline, 1H-Imidazole-1-ethanol, 4,5-dihydro-2-undecyl-,1H-Imidazole-1-ethanol, 2(-8-heptadecenyl)-4,5-dihydro,1-(2-hydroxyethyl)-2-tall oil alkyl-2-imidazoline, azelaic acid salt,1H-Imidazole-1-ethanol, 2-heptadecyl-4,5-dihydro,1H-Imidazole-1-ethanol, 2-nonyl-4,5-dihydro, 1H-Imidazole-1-ethanol,4,5-dihydro-2-C₁₅₋₁₇-unsaturated alkyl derivatives,1H-Imidazole-1-ethanol, 4,5-dihydro-2-norcoco alkyl derivatives,1H-Imidazole-1-ethanol, 4,5-dihydro-2-nortall-oil alkyl derivatives,reaction product of 4,5-dihydro-2-nonyl 1H-Imidazole-1-ethanol, and4,5-dihydro-2-heptyl 1H-Imidazole-1-ethanol with 2-propenoic acid,1-propane sulfonic acid, 3-chloro-2-hydroxy-mono sodium salt reactionproducts with 2-(8Z)-8-heptadecenyl-4,5-dihydro 1H-Imidazole-1-ethanol,chloroacetic acid sodium salt reaction products with1H-Imidazole-1-ethanol, 4,5-dihydro-2-norcoco alkyl derivatives, andsodium hydroxide, 2-(8-heptadecenyl)-4,5-dihydro1H-Imidazole-1-ethanamine, or the 9-octadecenoic acid compound with2-(8-heptadecenyl)-4,5-dihydro 1H-Imidazole-1-ethanamine.

Unless otherwise noted, an “alkyl having up to 30 carbon atoms,” as usedherein, refers to a branched or unbranched radical such as, for example,methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl or docosyl.

Unless otherwise noted, an “alkyl having 2 to 25 carbon atoms which isinterrupted by oxygen or sulfur,” refers to an alkyl having 2 to 25carbon atoms which can be interrupted one or more times, for example,CH₃—O—CH₂—, CH₃—S—CH₂—, CH₃—O—CH₂ CH₂—O—CH₂—, CH₃—(O—CH₂ CH₂—)₂ O—CH₂—,CH₃—(O—CH₂ CH₂—)₃ O—CH₂— or CH₃—(O—CH₂ CH₂—)₄ O—CH₂—.

Unless otherwise noted, an “alkyl having 3 to 25 carbon atoms which isinterrupted by oxygen or sulfur,” as used herein, refers to an alkylhaving 3 to 25 carbon atoms which can be interrupted one or more times,for example, CH₃—O—CH₂ CH₂—, CH₃—S—CH₂ CH₂—, CH₃—O—CH₂ CH₂—O—CH₂ CH₂—,CH₃—(O—CH₂ CH₂—)₂ O—CH₂ CH₂—, CH₃—(O—CH₂ CH₂—)₃ O—CH₂ CH₂— or CH₃—(O—CH₂CH₂—)₄ O—CH₂ CH₂—.

Unless otherwise noted, an “alkenyl having 2 to 24 carbon atoms,” asused herein, refers to a branched or unbranched radical, for example,vinyl, propenyl, 2-butenyl, 3-butenyl isobutenyl, n-2,4-pentadienyl,3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl,n-2-octadecenyl or n-4-octadecenyl.

C₄-C₁₅ Cycloalkyl, or C₅-C₁₅ cycloalkyl, which is unsubstituted orsubstituted by C₁-C₄ alkyl and/or carboxyl and which preferably contains1 to 3, or 1 or 2, branched or unbranched alkyl group radicals and/or 1or 2 carboxyl groups, can be, for example, cyclopentyl,methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, 2-carboxycyclohexyl,3-carboxycyclohexyl, methylcyclohexyl, dimethylcyclohexyl,trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl orcyclododecyl.

C₅-C₁₅ Cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyland/or carboxyl and which preferably contains 1 to 3, or 1 or 2,branched or unbranched alkyl group radicals and/or 1 or 2 carboxylgroups, can be, for example, cyclopentenyl, methylcyclopentenyl,dimethylcyclopentenyl, cyclohexenyl, 2-carboxycyclohexenyl,3-carboxycyclohexenyl, 2-carboxy-4-methylcyclohexenyl,methylcyclohexenyl, dimethylcyclohexenyl, trimethylcyclohexenyl,tert-butylcyclohexenyl, cycloheptenyl, cyclooctenyl or cyclododecenyl.It is preferably C₅-C₁₂ cycloalkenyl, in particular C₅-C₁₈ cycloalkenyl,e.g., cyclohexenyl.

C₁₃-C₂₆ Polycycloalkyl can be, for example, the C₁₃-C₂₆ polycycloalkylswhich occur in naphthenic acid [J. Buckingham, Dictionary of OrganicCompounds, Vol. 4, page 4152, 5th Edition (1982)].

C₇-C₉ Phenylalkyl which is unsubstituted or substituted on the phenylradical by C₁-C₄ alkyl and which preferably contains 1 to 3, inparticular 1 or 2, branched or unbranched alkyl group radicals can be,for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl 2-phenylethyl,2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl,2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.

A 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl and whichpreferably contains 1 to 3, in particular 1 or 2, branched or unbranchedalkyl or alkoxy group radicals, and preferably 1 to 3, in particular 1or 2, heteroatoms from the group consisting of nitrogen, oxygen andsulfur can be, for example, thienyl, 2-methylthienyl, 3-chlorothienyl,3-methoxythienyl, tetrahydrofuranyl, furyl, pyrrolidinyl,1-methylpyrrolidinyl, pyrrolyl, thiazolyl, isothiazolyl, imidazolyl,carboxyimidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyridyl,piperidinyl, morpholinyl, pyrazinyl, carboxypyrazinyl, piperazinyl,triazinyl or 2,6-dimethoxytriazonyl.

A 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxy and isbenzo-fused, which preferably contains 1 to 3, in particular 1 or 2,branched or unbranched alkyl or alkoxy group radicals and preferably 1to 3, in particular 1 or 2, heteroatoms from the group consisting ofnitrogen, oxygen and sulfur can be, for example, benzothiazolyl,5-chlorobenzothiazolyl, 5-methoxybenzothiazolyl, 5-methylbenzothiazolyl,benzoimidazolyl, benzooxazolyl, benzoisothiazolyl or benzothienyl.

Unless otherwise noted, an “alkoxy having up to 18 carbon atoms,” asused herein, refers to a branched or unbranched radical such as, forexample, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy,hexadecyloxy or octadecyloxy. C₁-C₂ alkoxy is preferred, in particularC₁-C₁₀ alkoxy, e.g. C₁-C₈ alkoxy.

C₂-C₁₈ Alkoxy which is interrupted by oxygen or sulfur can be, forexample, CH₃—O—CH₂ CH₂ O—, CH₃—S—CH₂ CH₂ O—, CH₃—O—CH₂ CH₂—O—CH₂ CH₂ O—,CH₃—S—CH₂ CH₂—S—CH₂ CH₂ O—, CH₃—S—CH₂ CH₂—O—CH₂ CH₂ O—CH₃—(O—CH₂ CH₂—)₂O—CH₂ CH₂ O—, CH₃—(O—CH₂ CH₂—)₃ O—CH₂ CH₂ O— or CH₃—(O—CH₂ CH₂—)₄ O—CH₂CH₂—.

Phenyl or naphthyl substituted by C₁-C₄ alkyl, which preferably contains1 to 3, in particular 1 or 2, alkyl groups, can be, for example, o-, m-or p-methylphenyl 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4tert-butylphenyl,2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl,4-methylnaphthyl, 1,6-dimethylnaphthyl or 4-tert-butylnaphthyl.

C₁₀-C₁₂ Naphthylalkyl which is unsubstituted or substituted on thenaphthyl ring system by C₁-C₄ alkyl and which preferably contains 1 to3, in particular 1 or 2, branched or unbranched alkyl group radicals canbe, for example, naphthylmethyl, α-methylnaphthylmethyl,α,α-dimethylnaphthylmethyl, naphthylethyl, 2-methyl-1-naphthylmethyl,3-methyl-1-naphthylmethyl, 4-methyl-1-naphthylmethyl,2,4-dimethyl-1-naphthylmethyl, 2,6-dimethyl-1-naphthylmethyl or4-tert-butyl-1-naphthylmethyl.

An unsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ringwhich preferably contains 1 to 3, in particular 1 or 2, branched orunbranched alkyl group radicals can be, for example, cyclopentylidene,methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene,methylcyclohexylidene, dimethylcyclohexylidene,trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene,cyclooctylidene, cyclodecylidene or cyclododecylidene. Preference isgiven to cyclohexylidene and tert-butylcyclohexylidene.

Unless otherwise noted, a “halogen,” as used herein, refers to chlorine,bromine or iodine, for example, chlorine.

Unless otherwise noted, a “haloalkyl having up to 25 carbon atoms,” asused herein, refers to a branched or unbranched radical such as, forexample, chloromethyl, chloroethyl, chloropropyl, chlorobutyl or3-chloro-1-butyl.

Unless otherwise noted, an “alkylthio having up to 18 carbon atoms,” asused herein, refers to a branched or unbranched radical such as, forexample, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio,isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio,octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio.Alkylthio having 1 to 12 carbon atoms is preferred, in particular 1 to 8carbon atoms, e.g. 1 to 6 carbon atoms. C₁-C₄ Alkyl-substituted phenoxyor naphthoxy, which preferably contains 1 to 3, in particular 1 or 2,alkyl groups, can be for example o-, m- or p-methylphenoxy,2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy,2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy,2,6-diethylphenoxy, 1-methylnaphthoxy, 2-methylnaphthoxy,4-methylnaphthoxy, 1,6-dimethylnaphthoxy or 4-tert-butylnaphthoxy.

C₇-C₉ Phenylalkoxy which is unsubstituted or substituted on the phenylring by C₁-C₄ alkyl, and preferably contains 1 to 3, in particular 1 or2, branched or unbranched allyl group radicals, can be for examplebenzyloxy, 2-phenylethoxy, 2-methylbenzyloxy, 3-methylbenzyloxy,4-methylbenzyloxy, 2,4-dimethylbenzyloxy, 2,6-dimethylbenzyloxy or4-tert-butylbenzyloxy. Benzyloxy is preferred.

C₁₀-C₁₂ Naphthylalkoxy which is unsubstituted or substituted on thenaphthyl ring system by C₁-C₄ alkyl, and preferably contains 1 to 3, inparticular 1 or 2, branched or unbranched alkyl group radicals, can befor example naphthylmethoxy, naphthylethoxy, 2-methyl-1-naphthylmethoxy,3-methyl-1-naphthylmethoxy, 4-methyl-1-naphthylmethoxy,2,4-dimethyl-1-naphthylmethoxy, 2,6-dimethyl-1-naphthylmethoxy or4-tert-butyl-1-naphthylmethoxy.

Unless otherwise noted, a “C₁-C₁₈ alkylene,” as used herein, refers to abranched or unbranched radical such as, for example, methylene,ethylene, propylene, tetramethylene, pentamethylene, hexamethylene,heptamethylene, octamethylene, decamethylene, dodecamethylene oroctadecamethylene.

Unless otherwise noted, a “C₂-C₁₈ alkylene which is interrupted byoxygen or sulfur,” as used herein, refers to a C₂-C₁₈ alkylene which canbe interrupted one or more times, for example —CH₂—O—CH₂—, —CH₂—S—CH₂—,—CH₂—NH—CH₂—, —CH₂—O—CH₂ CH₂—O—CH₂—, —CH₂—(O—CH₂ CH₂—)₂ O—CH₂—,—CH₂—(O—CH₂ CH₂—)₃ O—CH₂—, —CH₂—(O—CH₂ CH₂—)₄ O—CH₂— or —CH₂ CH₂—S—CH₂CH₂—.

Unless otherwise noted, a “C₄-C₁₈ alkylene interrupted by oxygen,sulfur, or an optionally alkyl-substituted nitrogen,” as used herein,refers to a C₄-C₁₈ alkylene, which can be interrupted one or more times,for example —CH₂ CH₂—NH—CH₂ CH₂—, —CH₂ CH₂—N(CH₃)—CH2 CH₂—, —CH₂CH₂—NH—CH₂ CH₂ CH₂—, —CH₂ CH₂—S—CH₂ CH₂—, —CH₂ CH₂—O—CH₂ CH₂—O—CH₂ CH₂—,—CH₂ CH₂ NH—CH₂ CH₂—NH—CH₂ CH₂ CH₂—, —CH₂ CH₂—(O—CH₂ CH₂—)₂ O—CH₂ CH₂—,—CH₂ CH₂—(O—CH₂ CH₂—)₃ O—CH₂ CH₂— or —CH₂ CH₂—(O—CH₂ CH₂—)₄ O—CH₂ CH₂—.

C₂-C₁₈ alkenylene can be, for example vinylene, methylvinylene,octenylethylene or dodecenylethylene. C₂-C₁₂ Alkenylene is preferred,especially C₂-C₈ alkenylene. C₂-C₁₈ alkenylene can be forexample—2-propynylene, 2-butynylene, 2-pentynylene, 2-hexynylene,3-hexynylene, 3-heptynylene, 2-decynylene, 4-decynylene or8-octadecynylene.

Alkylidene having 2 to 20 carbon atoms can be for example ethylidene,propylidene, butylidene, pentylidene, 4-methylpentylidene, heptylidene,nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene,1-ethylpropylidene or 1-ethylpentylidene.

Phenylallidene having 7 to 20 carbon atoms can be for examplebenzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene.

Unless otherwise indicated, a “C₅-C₉ cycloalkylene,” as used herein,refers to a saturated hydrocarbon group having two free valences and atleast one ring unit and can be, for example, cyclopentylene,cyclohexylene, cycloheptylene or cyclooctylene. Cyclohexylene ispreferred.

An Unsubstituted or C₁-C₄ alkyl-substituted phenylene or naphthylene canbe, for example, 1,2-, 1,3-, or 1,4-phenylene; or 1,2-, 1,3-, 1,4-,1,6-, 1,7-, 2,6-, or 2,7-naphthylene. 1,4-Phenylene is preferred.

In certain embodiments, the metal amidine complexes described herein areprepared by heating 1 mole of metal carboxylate with 4 moles of amidinein methanol. The mixture is held at about 50° C. for about 2 hours oruntil it becomes a clear solution. The clear solution is filtered anddried. In some embodiments, the dried catalyst is then optionallyblended with fumed silica. A suitable fumed silica is Sipernat 50S fromDegussa Corporation.

4.2 Epoxy Coating Compositions and Their Uses

In certain embodiments, provided herein is an epoxy compositioncomprising a polyepoxide, a polyacid curing agent, and one or morecatalyst composition comprising a metal amidine complex and one or moresecond compounds, as described herein. In certain embodiments, the epoxycomposition is film-forming. In certain embodiments, the polyepoxide isan epoxy-containing acrylic polymer, an epoxy condensation polymer(e.g., a polyglycidyl ether of an alcohol and/or a phenol), or apolyepoxide monomer or oligomer. In particular embodiment, thepolyepoxide is an epoxy-containing acrylic polymer.

In certain embodiments, the one or more catalyst composition is presentin the amount of 0.05 to about 10 wt. %, about 0.1 to about 10 wt. %,about 0.5 to about 10 wt. %, about 1 to about 10 wt. %, about 2 to about8 wt. %, about 2 to about 6 wt. %, about 2 to about 4 wt. %, or about 4to about 8 wt. %, based on the total weight of the coating composition.

In certain embodiments, the polyepoxide is a polylglycidyl ether ofbisphenol A or F or NOVOLAK™, or phenol formaldehyde resins with amolecular weight of about 350 to about 10000, more specifically fromabout 380 to about 4000. These resins may be used as solids or viscousliquids. In certain embodiments, diglycidyl esters of di andpolycarboxylic acids are used. In other embodiments, glycidyl functionalpolymers are used, including a polymer of the glycidyl ester ofmethacrylic acid, epoxidized oil, cycloaliphatic epoxies, or triglycidylisocyanurate. In certain embodiments, the polyepoxide is acycloaliphatic epoxy, for example 3,4-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate,spiro[1,3-dioxane-5,3′-[7]oxabicyclo[4.1.0]heptane],2-(7-oxabicyclo[4.1.0]hept-3-yl), 3,4-epoxycyclohexyl)methyl3,4-epoxycyclohexylcarboxylate, 1,2-epoxy-4-(epoxyethyl)cyclohexane,7-Oxabicyclo[4.1.0]heptane-3,4-dicarboxylic acid, bis(oxiranylmethyl)ester, 1,3,5-triglycidyl isocyanurate (TGIC), epoxidized soybean oil, orepoxidized linseed oil.

In certain embodiments, the epoxy-containing acrylic polymer is acopolymer of an ethylenically unsaturated monomer having at least oneepoxy group and at least one polymerizable ethylenically unsaturatedmonomer which is free of epoxy groups. In certain embodiments, theethylenically unsaturated monomer having at least one epoxy group is onehaving a 1,2-epoxy group (e.g., glycidyl acrylate, glycidylmethacrylate, and/or allyl glycidyl ether). In certain embodiments, theethylenically unsaturated monomer which is free of epoxy groups is analkyl ester of acrylic and methacrylic acid containing from 1 to 20carbon atoms in the alkyl group. In other embodiments, the ethylenicallyunsaturated monomer which is free of epoxy groups is a vinyl aromaticcompound (e.g., styrene and derivatives thereof), a vinyl nitrile (e.g.,acrylonitrile and derivatives thereof), a vinyl and vinylidene halide, avinyl ester, or mixtures thereof. In certain embodiments, theethylenically unsaturated monomer which is free of epoxy groups does notcomprise a carboxylic acid group.

In certain embodiments, the ethylenically unsaturated monomer having atleast one epoxy group is present in amounts of from about 5 to about 60,or from about 20 to about 50 percent by weight of the total monomersused in preparing the epoxy-containing acrylic polymer. In certainembodiments, the ethylenically unsaturated monomer which is free ofepoxy groups comprises one or more alkyl ester of acrylic andmethacrylic acid, in an amount from about 40 to about 95 percent, orfrom about 50 to about 80 percent by weight of the total monomers arethe alkyl esters of acrylic and methacrylic acid.

In certain embodiments, the epoxy-containing acrylic polymer is preparedby mixing the ethylenically unsaturated monomer having at least oneepoxy group and the at least one polymerizable ethylenically unsaturatedmonomer which is free of epoxy groups and reacting the mixture, forexample, by conventional free radical initiated organic solutionpolymerization.

In certain embodiments, the epoxy-containing acrylic polymer has anumber average molecular weight between about 1000 and about 20,000, orbetween about 1000 and about 10,000, or between about 1000 and about5000. In certain embodiments, the molecular weight is determined by gelpermeation chromatography using a polystyrene standard. In determiningmolecular weights in these embodiments, it is not the actual molecularweights which are measured but an indication of the molecular weight ascompared to polystyrene. The values which are obtained are commonlyreferred to as polystyrene numbers. However, as used herein, they aremolecular weights.

In certain embodiments, the polyepoxide is an epoxy condensationpolymer, that is, a polymer having a 1,2-epoxy equivalency greater than1, for example from about 1 to about 3.0. In various embodiments, thepolyepoxide is a polyglycidyl ether of a polyhydric phenol and/or analiphatic alcohols. Sich a polyepoxide can be produced by etherificationof the polyhydric phenol or aliphatic alcohol with an epihalohydrin suchas epichlorohydrin in the presence of alkali.

In certain embodiments, the polyhydric phenol is2,2-bis(4-hydroxyphenyl)propane (bisphenol A) or1,1-bis(4-hydroxyphenyl)ethane a bis(4-hydroxyphenyl)propane. In certainembodiments, the aliphatic alcohol is ethylene glycol, diethyleneglycol, 1,2-propylene glycol or 1,4-butylene glycol. In certainembodiments, the aliphatic alcohol is a cycloaliphatic polyol, forexample 1,2-cyclohexanediol, 1,4-cyclohexanediol,1,2-bis(hydroxymethyl)cyclohexane, or hydrogenated bisphenol A.

In other embodiments, the polyepoxide can be one of those described inU.S. Pat. No. 4,102,942 at column 3, lines 1-16, incorporated byreference herein. In particular embodiments, the polyepoxide is3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate orbis(3,4-epoxy-6-methylcyclohexyl-methyl) adipate. In certainembodiments, the polyepoxide is an epoxy-containing acrylic polymer. Insuch embodiments, the resultant product has a preferable combination ofcoating properties, i.e., smoothness, gloss, durability, and solventresistance. Such resultant polymers are useful, for example, in theformulation of clear coats for color-plus-clear applications.

In certain embodiments, the polyepoxide is one having a glass transitiontemperature less than about 50° C., for example less than about 30° C.The glass transition temperature (T_(g)) is described in PRINCIPLES OFPOLYMER CHEMISTRY, Flory, Cornell University Press, Ithaca, N.Y., 1953,pages 52-57. In certain embodiments, the T_(g) is calculated asdescribed by Fox in Bull. Amer. Physic. Soc., 1, 3, page 123 (1956),incorporated by reference herein. In certain embodiments, the T_(g) isdetermined experimentally, for example, by using a penetrometer such asa DuPont 940 Thermomedian Analyzer.

In a specific embodiment, the polyepoxide is a mixture ofepoxy-containing acrylic polymer (e.g., as described above) and a lowermolecular weight polyepoxide, such as an epoxy condensation polymer(e.g., as described above) having a molecular weight less than about800.

In certain embodiments, the polyepoxide is present in the composition inan amount from about 10 to about 90, or from about 25 to about 80 weightpercent based on total weight of resin solids. In embodiments where alower molecular weight polyepoxide is used (e.g., a molecular weightless than about 800), it is present in an amount from about 1 to about40, or from about 5 to about 30 percent by weight based on total weightof resin solids.

In certain embodiments, the polyacid curing agent includes two or moreacid groups per molecule. The acid groups are reactive with thepolyepoxide to form a crosslinked coating as indicated by its resistanceto organic solvent. In certain embodiments, the acid functionality is acarboxylic acid or a sulfonic acid. In various embodiments, the polyacidcuring agent includes carboxylic acid group-containing polymers such asacrylic polymers, polyesters, and polyurethanes, as well as oligomerssuch as ester group-containing oligomers and monomers. In a particularembodiment, the polyacid curing agent is a carboxyl-terminated materialhaving at least two carboxyl groups per molecule. In certainembodiments, the polyacid curing agent has a T_(g) less than 30° C. Suchlow T_(g) materials can, for example, enable the formation of highsolids liquid compositions. Higher T_(g) materials require the use ofmore solvent.

In certain embodiments, the polyacid curing agent is adipic acid;glutaric acid; glutaric anhydride; sebacic acid; 1,10 decanedioic acid;fumaric acid; maleic acid and maleic anhydride; succinic acid; phthalicacid and phthalic anhydride; 8,9,10-trinorborn-5-ene-2,3-dicarboxylicacid and 8,9,10-trinorborn-5-ene-2,3-dicarboxylic anhydride;cyclohexene-1,2-dicarboxylic acid; diphenyl-2,2′-dicarboxylic acid;methylnorbornene-2,3-dicarboxylic anhydride;cyclohexene-1,2-dicarboxylic acid; tetrahydrophthalic anhydride;5-methyltetrahydrophthalic anhydride;octahydro-4,7-methano-1H-indene-5,-dicarboxylic acid;1,2-cyclohexanedicarboxylic acid; a dimeric fatty acid; an alkenylsuccinic acid or anhydride; a dicarboxylic acid anhydride such assuccinic or glutaric anhydride; an alkenylsuccinate with an alkenylgroup from C6 to C18; an aromatic anhydride such as o-phthalicanhydride; trimellitic acid anhydride; or a linear anhydride of adiacid.

In embodiments where the polyacid curing agent is an acrylic polymer,copolymers of (a) an ethylenically unsaturated monomer containing atleast one carboxylic acid and (b) a different ethylenically unsaturatedmonomer which is free from carboxylic acid groups can be used. Incertain embodiments, the acrylic polymer preferably has an acid numberfrom about 30 to about 150, or from about 60 to about 120.

In certain embodiments, the (a) ethylenically unsaturated monomercontaining at least one carboxylic acid is acrylic acid, methacrylicacid, maleic acid or a partial ester of maleic acid. In certainembodiments, the (b) different ethylenically unsaturated monomer whichis free from carboxylic acid groups comprises the group

for example styrene, an alpha-substituted lower alkyl styrene (e.g.,alpha-methylstyrene), or an alkyl ester of an acrylic or methacrylicacids (e.g., methyl methacrylate, methyl and ethyl acrylate, or mixturesthereof).

In certain embodiments, the copolymer is prepared in conventionalfashion, e.g., by heating monomers (a) and (b) at elevated temperatures,for example from about 90 to about 140° C., or from about 115° C. toabout 125° C. The reaction may be carried out in bulk or in solutionusing such conventional solvents as aromatic hydrocarbons, for examplebenzene, toluene and xylene, or alcohols (e.g. butyl alcohol ormonoalkyl ethers of ethylene glycol) or the like. In certainembodiments, the polymerization is carried out in the presence of apolymerization catalyst, for example, peroxides such as benzoylperoxide, di-tertiarybutyl-peroxide, di-cumene peroxide and methyl-ethylketone peroxide, or other catalysts of the free-radical type.

In certain embodiments, the carboxylic acid group-containing acrylicpolymer will have a relatively low molecular weight, having have numberaverage molecular weights as determined by gel permeation chromatographyusing a polystyrene standard of from about 500 to about 5000, or fromabout 700 to about 3000. In certain embodiments, carboxylic acidgroup-containing acrylic polymer. In certain embodiments, the carboxylicacid group-containing acrylic polymer has a polydispersity value lessthan about 4, for example from about 2 to about 3. By “polydispersityvalue” is meant the ratio of the weight average molecular weight to thenumber average molecular weight, each being determined by gel permeationchromatography using a polystyrene standard as described above.

In certain embodiments, the carboxylic acid group-containing acrylicpolymer is obtained by polymerizing a carboxyl functional monomer suchas acrylic, methacrylic, maleic, fumaric, itaconic or the half ester ofmaleic or fumaric with acrylic or styrene or acrylonitrile monomer. Incertain embodiments, the carboxylic acid group-containing acrylicpolymer is one with anhydride groups such as the copolymers of acrylicmonomers with maleic or itaconic anhydride. Examples for tri carboxylicacids/anhydrides are 1-propene-1,2,3-tricarboxylic acid;1,2,4-benzenetricarboxylic acid; an adduct of abietic acid with fumaricacid or maleic anhydride; trimellitic anhydride; and citric acid.Examples for monoacids are the C₁₂ to C₁₈ fatty acids saturated andunsaturated.

The acid functional acrylic polymer impart sag control to the finalproduct. Certain clear film-forming compositions are high solidscompositions and have a tendency to sag when applied to verticalsurfaces. However, the acid functional acrylic polymers used with thecatalyst described herein surprisingly provides sag control to thecompositions.

In certain embodiments, the acid functional acrylic polymer is not thesole polyacid curing agent, and is used with the other polyacid curingagent, for example the half-ester described hereinbelow.

In other embodiments, the polyacid curing agent is an acidgroup-containing polyester. In certain embodiments, such polyester isformed by reacting a polyol with a polycarboxylic acid or anhydride.

With regard to the polyol-polycarboxylic acid or polycarboxylic acidanhydride, various polyols can be used including ethylene glycol,neopentyl glycol, glycerol, pentaerythritol, trimethylolpropane, and thelike. In pother embodiments, acid group-containing polyols such asdimethylolpropionic acid can be used.

In certain embodiments, polycarboxylic acids may be employed, forexample dicarboxylic acids such as phthalic acid, tetrahydrophthalicacid, hexahydrophthalic acid, maleic acid, itaconic acid, adipic acid,sebacic acid, or the like. In certain embodiments, anhydrides of thepolycarboxylic acids may be used.

The preparation of acid group-containing polyesters is well known in theart and usually involves preparation in organic solvent with sufficientacid group-containing ingredients to form an acid group-containingmaterial at the completion of the reaction. A sufficient excess of theacid component is employed in forming the polymers to provide an acidvalue of from about 10 to about 120, or from about 30 to about 60.

In certain embodiments, ester group-containing oligomers can be used,for example half-esters (e.g., those formed from reacting polyols and1,2-acid anhydrides). In certain embodiments, half-esters result in theformulation of high solids fluid compositions while maintainingoutstanding properties such as gloss and distinctness of image.

In certain embodiments, the half-ester is obtained by reaction between apolyol and a 1,2-acid anhydride under conditions sufficient to ring openthe anhydride forming the half-ester with substantially nopolyesterification occurring. In certain embodiments, such reactionproducts are of relatively low molecular weight with low polydispersityvalues and provide lower volatile organic contents in the coatingcomposition while still providing for excellent properties in theresultant coating. By substantially no polyesterification occurring itis meant that the carboxyl groups of the anhydride are not esterified bythe polyol in a recurring manner. By this is meant that less than about10, for example less than about 5 percent by weight polyester is formed.

Two reactions may occur in combining the anhydride and the polyoltogether under suitable reaction conditions. The desired reaction modeinvolves ring opening the anhydride ring with hydroxyl, i.e.

where X is the residue of the polyol after reaction with the1,2-dicarboxylic acid anhydride, R is an organic moiety associated withanhydride, and A is equal to at least 2. Subsequently, carboxyl groupsformed by opening of the anhydride ring may react with hydroxyl groupsto give off water via a condensation reaction. This latter reaction isnot desired since it can lead to a polycondensation reaction resultingin products with higher molecular weights

To achieve the desired reaction, the 1,2-acid anhydride and polyol arecontacted together usually by mixing the two ingredients together in areaction vessel. In certain embodiments, the reaction is conducted inthe presence of an inert atmosphere such as nitrogen and in the presenceof a solvent to dissolve the solid ingredients and/or to lower theviscosity of the reaction mixture. Examples of suitable solvents arehigh boiling materials and include, for example, ketones such as methylamyl ketone, diisobutyl ketone, methyl isobutyl ketone; aromatichydrocarbons such as toluene and xylene; as well as other organicsolvents such as dimethyl formamide and N-methyl-pyrrolidone.

For the desired ring opening reaction and half-ester formation, a1,2-dicarboxylic anhydride is used. Reaction of a polyol with acarboxylic acid instead of an anhydride would require esterification bycondensation eliminating water which would have to be removed bydistillation. Under these conditions this would promote undesiredpolyesterification. In certain embodiments, the reaction temperature ispreferably low, that is, no greater than about 135° C., for example lessthan about 120° C., or within the range of about 70° to about 135° C.,or from about 90° to about 120° C. Temperatures greater than 135° C. areundesirable because they promote polyesterification, whereastemperatures less than 70° C. are undesirable because of sluggishreaction. The time of reaction can vary somewhat depending principallyupon the temperature of reaction. In certain embodiments, the reactiontime will be from as low as about 10 minutes to as high as about 24hours.

In certain embodiments, the equivalent ratio of anhydride to hydroxy onthe polyol is at least about 0.8:1 (the anhydride being consideredmonofunctional) to obtain maximum conversion to the desired half-ester.In other embodiments, ratios less than 0.8:1 are used be used; suchratios result in increased formation of half-esters.

In certain embodiments, the anhydride which can be used in the formationof the polyesters is one which, exclusive of the carbon atoms and theanhydride moiety, contains from about 2 to 30 carbon atoms—for example,aliphatic, including cycloaliphatic, olefinic and cycloolefinicanhydrides and aromatic anhydrides. Substituted aliphatic and aromaticanhydrides are also included within the definition of aliphatic andaromatic provided the substituents do not adversely affect thereactivity of the anhydride or the properties of the resultantpolyester. Examples of substituents include chloro, alkyl and alkoxy. Incertain specific embodiments, the anhydride is succinic anhydride,methylsuccinic anhydride, dodecenyl succinic anhydride,octadecenylsuccinic anhydride, phthalic anhydride, tetrahydrophthalicanhydride, methyltetrahydrophthalic anhydride, hexahydrophthalicanhydride, an alkyl hexahydrophthalic anhydrides such asmethylhexahydrophthalic anhydride, tetrachlorophthalic anhydride,endomethylene tetrahydrophthalic anhydride, chlorendic anhydride,itaconic anhydride, citraconic anhydride, or maleic anhydride.

In certain embodiments, the polyol which can be used is one whichcontains from about 2 to about 20 carbon atoms, or from about 2 to about10 carbon atoms for example diols, triols and mixtures thereof. Incertain embodiments, the polyol is an aliphatic polyol such as ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,1,5-pentanediol, glycerol, 1,2,3-butanetriol, 1,6-hexanedial, neopentylglycol, diethylene glycol, dipropylene glycol,1,4-cyclohexanedimethanol, trimethylolpropane,2,2,4-trimethylpentane-1,3-diol, pentaerythritol, or tetrol. In certainembodiments, the polyol is an aromatic polyols, such as bisphenol A andbis(hydroxymethyl) xylene.

In certain embodiments, the polyacid curing agent is a mono, di or polyglycidyl ester (e.g., the reaction products of a mono, di orpolycarboxylic acid with epichlorohydrin); a glycidyl ether of analiphatic ether of a diol, triol and/or polyol (e.g., 1,2,3-propanetriolglycidyl ether); an alkyl (C₁₀-C₁₆) glycidyl ether; a lauryl glycidylether; a glycerin 1,3-diglycidyl ether; an ethylene diglycidyl ether; apolyethylene glycol bis(glycidyl ether); a 1,4-butanediol diglycidylether; a 1,6-hexanediglycidyl ether; a bis(2,3-epoxypropyl)ether; a homoor copolymer of an allyl glycidyl ether; or an ethoxylatedalcohol(C₁₂-C₁₄) glycidyl ether. In certain embodiments, the polyacid isa phenyl glycidyl ether, a p-t-butylphenol glycidyl ether, ahydroquinone diglycidyl ether, a glycidyl p-glycidyloxybenzoate, ap-nonylphenol glycidyl ether, or a glycidyl ether reaction product of2-methyl phenol and formaldehyde polymer.

In certain embodiments, monomers containing at least two acid groups canbe used, for example monomeric polycarboxylic acids containing fromabout 5 to about 20 carbon atoms and may be open chain, cyclic,saturated, unsaturated and aromatic acids. In certain embodiments, themonoer is succinic acid, adipic acid, azelaic acid, sebacic acid,hexahydrophthalic acid, maleic acid, cyclohexene-1,2-dicarboxylic acid,or phthalic acid.

In certain embodiments, the polyacid curing agent is present in thecoating composition in an amount from about 10 to about 90, or fromabout 25 to about 75 percent by weight based on total weight of resinsolids.

In certain embodiments, the polyepoxide-polyacid composition furthercomprise an anhydride, for example an anhydride which is a liquid at 25°C. The presence of such an anhydride in the compositions may provide animproved cure response. In certain embodiments, the anhydride is analkyl-substituted hexahydrophthalic anhydrides wherein the alkyl groupcontains up to 7 carbons, or up to 4 carbons (such as methylhexahydrophthalic anhydride) or dodecenyl succinic anhydride. In certainembodiments, the anhydride is present in an amount from about 0 to about40, or from about 5 to about 25 percent by weight based on total weightof resin solids.

In certain embodiments, the equivalent ratio of carboxyl to epoxy in theclear film-forming compositions is such that there are from about 0.3 toabout 3.0, or from about 0.8 to about 1.5 equivalents of carboxyl(anhydride being considered monofunctional) per equivalent of epoxy.

In certain embodiments, the ratio of the epoxy compound to the carboxylor anhydride in the formulation is from about 0.5 to 1 to about 5 to 1.It will be understood that the ratio can be modified depending on thecrosslinking density desired. For example, and without intending to belimited by mechanism in any way, the desired crosslinking density isachieved when the ratio of functional epoxy groups and carboxyl groupsis 1 to 1 under ideal conditions. However, with most epoxy formulationssome self-condensation of the epoxy groups takes place. For example, itis may be necessary to use an excess of epoxy groups to react all thecarboxyl or anhydride groups so that a film with no free carboxyl groupsare present, if excellent detergent or alkali resistance in a film isdesired. However, if better adhesion and flexibility is desired, thenthe ratio can be adjusted so that some of the unreacted carboxyl groupsremain.

Again without intending to be limited by mechanism, it is believed thatthe ratio of epoxy to carboxyl functional groups is important for primerapplications where corrosion resistance is an important requirement. Insuch a formulation the level of epoxy resin can be reduced. The ratio ofepoxy to carboxyl groups is also dependent on the functional groups inthe reactant system. For example, if one reacts a carboxyl functionalacrylic resin with a difunctional epoxy resin, it might be desirable touse an excess of carboxyl groups. If an acrylic resin which has a highmolecular weight is used, it usually contains many carboxyl groups; atypical acrylic resin might have an acid number of 56 and a molecularweight of 20,000. In such a resin the average chain contains 20 carboxylgroups. To achieve crosslinking in such a system, theoretically threecarboxyl groups have to be reacted to form an effective network. Theepoxy in such a formulation might be diglycidyl ether of bisphenol A, adifunctional crosslinker. A person with skill in the coating art wouldtherefore use an excess of carboxyl groups and a deficiency of epoxygroups to achieve a good network. Most crosslinking reactions do not goto completion. If the crosslinkers have reacted to an average to 75%, itindicates that some molecules of the crosslinking agents have completelyreacted, with some molecules having reacted only at one end and somemolecules having not reacted at all. By having an excess of carboxylgroups on the acrylic, one could assure a higher conversion of all theepoxy groups. This problem is typical in can coatings, where it isimportant to eliminate any unreacted epoxy resin to prevent any leachingof epoxy resin into the food.

In certain embodiments, the polyepoxide-polyacid compositions furthercomprises a silane functionality, which can be incorporated into thecomposition, for example, by using a reactive silane group-containingmaterial (such as gamma-methacryloxypropyltrimethoxysilane ormercaptopropyltrimethoxysilane) in the preparation of the epoxygroup-containing acrylic polymer. Such materials co-react with thepolymerizing monomers or polymers forming a polymer with silane curinggroups. In certain embodiments, the composition comprises a silanegroup-containing material, such as methyltrimethoxysilane.

In certain embodiments, the composition further comprises one or more ofthe following optional ingredients: an auxiliary curing agent such asaminoplasts, a plasticizer, an anti-oxidant, and a UV light absorbers.These ingredients typically are present in amounts of up to 25 percentby weight based on total resin weight.

In certain embodiments, the polyepoxide-polyacid composition is a liquidcomposition, for example a liquid composition formulated into a liquidhigh solids coating composition. These coating compositions containgreater than about 40, or greater than about 50 percent, or greater thanabout 60 percent by weight resin solids. The solids content isdetermined by heating the composition to 105-110° C. for 1 to 2 hours todrive off the volatile material.

In certain embodiments, the composition is applied to a base coatedsubstrate by any of the conventional coating techniques such asbrushing, spraying, dipping or flowing. In a particular embodiment, thecomposition is applied to a base coated substrate by spray applications.Any of the known spray techniques may be employed such as compressed airspraying, electrostatic spraying and either manual or automatic methods.

After application of the top coat composition to the base coat, thecoated substrate is heated to cure the coating layers. In the curingoperation, solvents are driven off and the film-forming material of thetop coat and/or of the base coat is crosslinked with the aid of anycrosslinking agents present. In certain embodiments, the heating orcuring operation is carried out at a temperature in the range of fromabout 160° to about 350° F. (71°-177° C.). In certain embodiments, thethickness of the top coat is from about 0.5 to about 5 mm, or from about1.2 to about 3 mm.

In certain embodiments, the epoxy formulation is cured at a temperaturefrom about 100 to about 300° C., or from about 120 to about 250° C. Incertain embodiments, the epoxy formulation is cured for a time periodfrom about 2 seconds to about 4 hours, or from about 30 seconds to about30 minutes.

In certain embodiments, the epoxy compositions provided herein areuseful for producing coatings, adhesive films, or in casting or molding.For example, specific applications include use as corrosion resistantprimers for automotive applications, or can or coil coatings, orautomotive clear coats. The coatings can be applied as a high solids ora powder coating.

In certain embodiments, the metal amidine complex and second compoundare, respectively, Zn(1-methylimidazole)₂(acetate)₂ and DABCO;Zn(1-methylimidazole)₂(acetate)₂ and zinc acetylacetonate;Zn(1-methylimidazole)₂(acetate)₂ and dibutyltin dilaurate;Zn(1-methylimidazole)₂(acetate)₂ and zirconium acetylacetonate;Zn(1-Methylimidazole)₂(2-Ethylhexanoate)₂ and a bismuth carboxylate;Zn(1,1,3,3-Tetramethylguanidine)₂(2-Ethylhexanoate)₂ and a bismuthcarboxylate; Zn(1-methylimidazole)₂(acetate)₂ and a bismuth carboxylate;Zn(1-methylimidazole)₂(acetate)₂ and lithium neodecanoate;Zn(2-Ethylhexanoate)₂(acetate)₂ and phenylmercuric acetate;Zn(1-methylimidazole)₂(acetate)₂ and dinonylnaphthalene disulfonate;Zn(1-methylimidazole)₂(acetate)₂ and 1,2-dimethylimidazole; orZn(1-methylimidazole)₂(acetate)₂ and 2-methylimidazole.

In related embodiments, provided herein is a method of coating asubstrate, comprising applying to a substrate an epoxy compositioncomprising a polyepoxide, a polyacid curing agent, and one or morecatalyst composition comprising a metal amidine complex and one or moresecond compounds, as described herein, and curing the coated substrate.Each of the components of the epoxy composition in this method aredescribed more fully hereinabove.

4.3 Polyurethane Coating Compositions and Their Uses

In certain embodiments, provided herein is a polyurethane powder coatingcomposition comprising:

Component A) a binder component which is solid below 40° C. and liquidabove 130° C. and has an OH number of 25 to 200 and a number averagemolecular weight of 400 to 10,000;

Component B) a hardener which is solid below 40° C. and liquid above125° C., contains uretdione groups and optionally free isocyanate groupsand is prepared from aliphatic and/or cycloaliphatic diisocyanates; and

Component C) one or more catalyst compositions comprising a metalamidine complex and a second compound, as described herein.

In certain embodiments, components A and B are present in amounts suchthat component B has about 0.6 to about 1.4 isocyanate groups for eachhydroxyl group present in component A and the amount of component C isabout 0.05 to about 10 wt. %, about 0.1 to about 10 wt. %, about 0.5 toabout 10 wt. %, about 1 to about 10 wt. %, about 2 to about 8 wt. %,about 2 to about 6 wt. %, about 2 to about 4 wt. %, or about 4 to about8 wt. %, based on the total weight of the coating composition.

In certain embodiments, this polyurethane powder coating is used forcoating heat-resistant substrates.

In certain embodiments, component A is a binder containing hydroxylgroups known from powder coating technology, for example polyesters,polyacrylates or polyurethanes containing hydroxyl groups. Mixtures ofsuch resins are also suitable. Examples of such resins, or mixturesthereof, can be found, for example, in U.S. Pat. No. 4,463,154 (toDisteldorf et al.) and U.S. Pat. No. 4,900,800 (to Halpaap et al.), eachhereby incorporated by reference herein in their entirety.

In certain embodiments, component B is a hardener containing uretdionegroups and optionally free isocyanate groups. The uretdiones can bederived from a broad range of isocyanates. In certain embodiments, theuretdione is derived from one or more of the following isocyanates:isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylenediisocyanate/2,4,4-trimethylhexamethylene diisocyanate (TMDI),norbornane diisocyanate (NBDI), methylenediphenyl diisocyanate (MDI),tetramethylxylylene diisocyanate (TMXDI),4,4′-diisocyanatodicyclohexylmethane, or1,3-diisocyanato-2(4)-methylcyclohexane. In particular embodiments,component B is derived from HDI or IPDI.

In certain embodiments, component C is a catalyst composition comprisinga metal amidine complex and a second compound, where the metal amidinecomplex and the second compound are, respectively:Zn(1-methylimidazole)₂(acetate)₂ and DABCO;Zn(1-methylimidazole)₂(acetate)₂ and zinc acetylacetonate;Zn(1-methylimidazole)₂(acetate)₂ and dibutyltin dilaurate;Zn(1-methylimidazole)₂(acetate)₂ and zirconium acetylacetonate;Zn(1-Methylimidazole)₂(2-Ethylhexanoate)₂ and a bismuth carboxylate;Zn(1,1,3,3-Tetramethylguanidine)₂(2-Ethylhexanoate)₂ and a bismuthcarboxylate; Zn(1-methylimidazole)₂(acetate)₂ and a bismuth carboxylate;Zn(1-methylimidazole)₂(acetate)₂ and lithium neodecanoate;Zn(2-Ethylhexanoate)₂(acetate)₂ and phenylmercuric acetate;Zn(1-methylimidazole)₂(acetate)₂ and dinonylnaphthalene disulfonate;Zn(1-methylimidazole)₂(acetate)₂ and 1,2-dimethylimidazole; orZn(1-methylimidazole)₂(acetate)₂ and 2-methylimidazole.

In certain embodiments, the powder coating compositions furthercomprises one or more component D, additives known from powder coatingtechnology. In various embodiments, component D optionally comprises oneor more leveling agent (e.g., polyvinyl, polybutyl acrylate, or thosebased on polysilicones), one or more light stabilizer (e.g., asterically hindered amines), one or more UV absorbers (e.g., ahydroxyphenyl triazine, a hydroxyphenyl benzotriazole, or abenzophenone), one or more pigment (e.g., titanium dioxide), one or morecolor stabilizer to counter yellowing due to overbake, (e.g., a trialkyland/or triaryl phosphite, optionally containing inert substituents, suchas triethyl phosphite, triphenyl phosphite and trisnonylphenylphosphite), and/or other auxiliaries, as described, for example, in EP669 353, incorporated herein by reference. In certain embodiment, thetotal amount of component(s) D ranges from about 0.05 to about 5% byweight, for example about 0.1, about 0.2, about 0.5, about 1, about 2,about 3, or about 4% by weight. In certain embodiments, fillers and/orpigments (e.g., titanium dioxide) are present in an amount of up to 50%by weight of the total composition.

In certain embodiments, the powder coating composition optionallyfurther comprises component E, which are acid scavengers. In certainembodiments, the acid scavengers react at elevated temperatures with theexcess acid functionality present in the starting hydroxyl functionalbinder. The acid scavengers are able to either neutralize the freecarboxylic acid functionality left in the binder resin, or react withthe free carboxyl group resulting in the formation of esters. In certainembodiments, the acid scavenger is an epoxy compound, a carbodiimide, a2-oxazoline, or a trialkyl orthoformate. In specific embodiments, theepoxy compound acid scavenger is aglycidyl ether of bisphenol A or F orNOVOLAK™, or aphenol formaldehyde resin with a molecular weight of about350 to about 10000, preferably between 380 and 4000. These resins may beused as solids or viscous liquids. In other embodiments, the acidscavenger is a mono-, di- and/or poly-glycidyl ester; the reactionproduct a mono-, di- and/or polycarboxylic acid with epichlorohydrin; aglycidyl ether or aliphatic ether of a diol, triol and/or polyol, suchas 1,2,3-propanetriol glycidyl ether; an alkyl (C₁₀-C₁₆) glycidyl ether;a lauryl glycidyl ether; a glycerin 1,3-diglycidyl ether; an ethylenediglycidyl ether; apolyethylene glycol bis(glycidyl ether); a1,4-butanediol diglycidyl ether; a 1,6-hexanediglycidyl ether;abis(2,3-epoxypropyl)ether; a homo or copolymers of an allyl glycidylether; or an ethoxylated alcohol(C₁₂-C₁₄) glycidyl ether.

In certain embodiments, the acid scavenger is a glycidyl ether ofbisphenol A and F or of phenol formaldehyde polymers. In certainembodiments, the acid scavenger is a phenyl glycidyl ether, ap-t-butylphenol glycidyl ether, a hydroquinone diglycidyl ether, aglycidyl p-glycidyloxybenzoate, a p-nonylphenol glycidyl ether, or aglycidyl ether reaction product of 2-methyl phenol and formaldehydepolymer.

In certain embodiments, the acid scavenger is a diglycidyl ester of adi- and/or polycarboxylic acids. In certain embodiments, the acidscavenger is a glycidyl functional polymer such as a glycidyl ester ofmethacrylic acid, a glycidyl ester of an epoxidized oil, a glycidylester of a cycloaliphatic epoxy compound, or triglycidyl isocyanurate.In certain embodiments, the cycloaliphatic epoxy compound is3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate;spiro[1,3-dioxane-5,3′-[7]oxabicyclo[4.1.0]heptane],2-(7-oxabicyclo[4.1.0]hept-3-yl), 3,4-epoxycyclohexyl)methyl3,4-epoxycyclohexylcarboxylate; 1,2-epoxy-4-(epoxyethyl)cyclohexane;7-Oxabicyclo[4.1.0]heptane-3,4-dicarboxylic acid, bis(oxiranylmethyl)ester; 1,3,5-triglycidyl isocyanurate (TGIC); epoxidized soybean oil; orepoxidized linseed oil.

In certain embodiments, the acid scavenger is an epoxy compound, forexample Araldite PT 810(TGIC), Araldite 912 (a mixture of terephthalicacid diglycidylester and trimellitic acid triglycidylester), Epikote 828(Bisphenol A diglycidyl ether), or Erisys GE-30 (trimethylolpropanetriglycidylether) (TMPTGE). In certain embodiments, the acid scavengeris an oxazoline, for example phenylenebisoxazoline,2-methyl-2-oxazoline, 2-hydroxyethyl-2-oxazoline,2-hydroxypropyl-2-oxazoline, or 5-hydroxypentyl-2-oxazoline. In certainembodiments, the acid scavenger is a carbodiimide, for example PicassianXL-701, a multifunctional polycarbodiimide. In certain embodiments, theacid scavenger is a single compound; in other embodiments the acidscavenger is a mixture of two or more compounds.

Component E) may be employed, for example, when acid groups are presentin the powder coating composition. In certain embodiments where suchacid groups are present in the powder coating composition, the amount ofcomponent E) in the composition is such that for each acid group thereare about 0.1 to about 10 acid-scavenging units of component E). Incertain embodiments, this ratio is about 0.2, about 0.5, about 1, about2, about 3, about 5, or about 8 acid-scavenging units of component E)for each acid group. In certain embodiments, the composition comprisesan additional catalyst, such as benzyltrimethylammonium chloride, forexample to accelerated the acid scavenging reaction.

In certain embodiments, the finished powder coating composition isproduced by intimately mixing components A, B, C, and optionally Dand/or E in an edge runner mill and homogenizing the mixture in anextruder at temperatures up to a maximum of 130° C. After cooling, theextrudate is fractionated and ground with a pin mill to a particle sizeof <100 μm. In certain embodiments, the powder prepared in this way isapplied with an electrostatic powder spraying unit at 60 kV to degreasediron panels which are then baked in a circulating air drying cabinet attemperatures between 150° and 200° C. for 20 minutes. Good solvent andchemical resistance may be obtained at considerably lower bakingtemperatures or shorter baking times than with comparable uretdionepowder coating compositions formulated without the catalysts describedherein. In addition, the cured films may be non-yellowing.

In related embodiments, provided herein is a method of coating asubstrate, comprising applying to a substrate a polyurethane powdercoating composition as described hereinabove, and curing the coatedsubstrate. Each of the components of the polyurethane powder coatingcomposition are described more fully hereinabove.

Polyurethane Electrocoating Compositions and Their Uses

In certain embodiments, provided herein is an electrocoating compositioncomprising (a) an active hydrogen-containing resin; (b) a cappedpolyisocyanate curing agent; and (c) a catalyst composition comprising ametal amidine complex and one or more second compounds, as describedherein. In certain embodiments, component (c) is present in a totalamount of from about 0.5 to about 10 parts, about 0.5 to about 5 parts,about 0.5 to about 4 parts, about 0.5 to about 3 parts, or about 0.5 toabout 2 parts per 100 parts by weight of the resin solid content in theelectrocoating composition.

In certain embodiments, component (c) is a catalyst compositioncomprising a metal amidine complex and a second compound, where themetal amidine complex and the second compound are, respectively:Zn(1-methylimidazole)₂(acetate)₂ and DABCO;Zn(1-methylimidazole)₂(acetate)₂ and zinc acetylacetonate;Zn(1-methylimidazole)₂(acetate)₂ and dibutyltin dilaurate;Zn(1-methylimidazole)₂(acetate)₂ and zirconium acetylacetonate;Zn(1-Methylimidazole)₂(2-Ethylhexanoate)₂ and a bismuth carboxylate;Zn(1,1,3,3-Tetramethylguanidine)₂(2-Ethylhexanoate)₂ and a bismuthcarboxylate; Zn(1-methylimidazole)₂(acetate)₂ and a bismuth carboxylate;Zn(1-methylimidazole)₂(acetate)₂ and lithium neodecanoate;Zn(2-Ethylhexanoate)₂(acetate)₂ and phenylmercuric acetate;Zn(1-methylimidazole)₂(acetate)₂ and dinonylnaphthalene disulfonate;Zn(1-methylimidazole)₂(acetate)₂ and 1,2-dimethylimidazole; orZn(1-methylimidazole)₂(acetate)₂ and 2-methylimidazole.

In certain embodiments, the active hydrogen-containing ionic resin isanionic or cationic. Without being limited in any way, it is believedthat cationic resins usually provide superior corrosion resistancecompared to anionic resins. In certain embodiments, the active hydrogensassociated with the ionic resins are those which are reactive withisocyanate groups, for example hydroxyl, primary amino, secondary amino,and thiol groups, including mixtures thereof. In certain embodiments,the active hydrogen-containing resin is a cation resin having amine saltgroups, for example acid-solubilized reaction products of polyepoxidesand primary or secondary amines, such as those described in U.S. Pat.Nos. 3,663,389; 3,922,253; 3,984,299; 3,947,388; 3,947,339; and4,031,050, herein incorporated by reference in their entirety.

In certain embodiments, the cation resin having amine salt groups is (i)an addition product between a polyepoxide compound and a primary mono-or polyamine, a secondary mono- or polyamine, or a primary and secondarymixed polyamine (see, for example, U.S. Pat. No. 3,984,299, incorporatedby reference herein); (ii) an addition product between a polyepoxidecompound and a secondary mono- or polyamine having a primary amino groupconverted into a ketimine form (see, for example U.S. Pat. No.4,017,438, incorporated by reference herein); or (iii) a reactionproduct obtained by etherification between a polyepoxide compound and ahydroxy compound having a primary amino group converted into a ketimineform (see, for example, Japanese Patent Application Kokai (Laid-Open)No. 43013/1984, incorporated by reference herein). In certainembodiments, the polyepoxide compound used in the production of theamine-added epoxy resin has at least two epoxy groups in the moleculeand preferably has a number-average molecular weight of generally atleast about 200, for example from about 400 to about 4,000, or fromabout 800 to about 2,000. In a specific embodiment, the polyepoxide is acompound obtained by a reaction between a polyphenol compound andepichlorohydrin. In certain embodiments, this polyphenol compound isbis(4-hydroxyphenyl)-2,2-propane; 4,4-dihydroxybenzophenone;bis(4-hydroxyphenyl)-1,1-ethane; bis(4-hydroxyphenyl)-1,1-isobutane;bis(4-hydroxy-tert-butylphenyl)-2,2-propane;bis(2-hydroxynaphthyl)methane; 1,5-dihydroxynaphthalene;bis(2,4-hydroxyphenyl)methane; tetra(4-hydroxyphenyl)-1,1,-2,2-ethane;4,4-dihydroxydi-phenyl-sulfone; phenolic novolac, or cresylic novolac.In certain embodiments, the polyepoxide compound is partially reactedwith a polyol, a polyether polyol, a polyester polyol, a polyamideamine,a polycarboxylic acid, a polyisocyanate compound, or the like. Incertain embodiments, the polyepoxide compound is graft-polymerized withε-caprolactone, an acrylic monomer, or the like.

In certain embodiments, an active hydrogen-containing ionic resin is acationic acrylic resins, such as those described in U.S. Pat. Nos.3,455,806 and 3,928,157, incorporated by reference herein in theirentirety. In certain embodiments, the active hydrogen-containing ionicresin is a cationic polyester resins, for example one containing ionicgroups and active hydrogen groups.

In certain embodiments, the active hydrogen-containing ionic resin isone having one or more quaternary ammonium salt groups, for example,those which are formed from reacting an organic polyepoxide with atertiary amine salt, such as described in U.S. Pat. Nos. 3,962,165;3,975,346; 4,001,101; and 4,101,486, which are incorporated herein byreference in their entirety. In certain embodiments, the activehydrogen-containing ionic resin is one having one or more ternarysulfonium salt groups and/or one or more quaternary phosphonium saltgroups, such as those described in U.S. Pat. Nos. 3,793,278 and3,984,922, respectively, each of which is incorporated herein byreference in its entirety.

In a particular embodiment, the active hydrogen-containing resin is acationic resins having primary and/or secondary amine groups, forexample those described in U.S. Pat. Nos. 3,663,389; 3,947,339 and4,116,900, which are incorporated herein by reference in their entirety.In U.S. Pat. No. 3,947,339, a polyketimine derivative of a polyaminesuch as diethylenetriamine or triethylenetetraamine is reacted with apolyepoxide. When the reaction product is neutralized with acid anddispersed in water, free primary amine groups are generated. Also,equivalent products are formed when polyepoxide is reacted with excesspolyamines such as diethylenetriamine and triethylenetetramine and theexcess polyamine vacuum stripped from the reaction mixture. Suchproducts are described in U.S. Pat. Nos. 3,663,389 and 4,116,900, whichare incorporated herein by reference in their entirety. All of the aboveare active hydrogen-containing resins in certain embodiments of theelectrocoating composition.

In certain embodiments, the active hydrogen-containing resins aremodified by chain-extending the polyepoxide to increase its molecularweight, such as described in U.S. Pat. No. 4,148,772 (in which thepolyepoxide is chain-extended with a polyester polyol) and in U.S. Pat.No. 4,468,307 (in which the polyepoxide is chain-extended with aparticular polyether polyol), each of which is incorporated by referencein its entirety. In certain embodiments, the chain extension methodsdescribed in Canadian Patent 1,179,443, incorporated by referenceherein, can be used.

In certain embodiments, a polyepoxide is used in preparing the cationicresins. In certain embodiments, the polyepoxide is a polymer having anepoxy equivalency greater than 1, for example about 2 or more. Incertain embodiments, the polyepoxide contains 1,2-epoxide groups and isdifunctional with regard to epoxy. In a specific embodiment, thepolyepoxide is a polyglycidyl ether of a cyclic polyol or a polyglycidylether of a polyphenol such as bisphenol A. In certain embodiments, thepolyepoxide is an acrylic polymers having epoxy groups. These polymerscan be formed by polymerizing an unsaturated epoxy group-containingmonomer such as glycidyl acrylate or glycidyl methacrylate with one ormore polymerizable ethylenically unsaturated monomers. Examples of thesepolymers are described in U.S. Pat. No. 4,001,156, which is incorporatedby reference herein.

In certain embodiments, the cationic resin can be prepared by reacting abisphenol A type epoxy resin with an epoxy equivalent weight of fromabout 200 to about 2000, for example from about 400 to about 1000, withan amine. In certain embodiments, this amine is ammonia, a primaryamine, a secondary amine, or a tertiary amine. In embodiments whereammonia is used in the preparation of the cationic resin, the reactionof the epoxy resin with ammonia is conducted in the presence of largeexcess of free ammonia to suppress gelation of the resin. In thisreaction a combination of primary, secondary and tertiary aminefunctional resin is formed. In embodiments where primary amines areused, depending on the ratio of amine to epoxy, secondary and tertiaryamine functional resins are formed. In embodiments where secondaryamines are used, tertiary amine functional resins are produced. If anexcess of epoxy is used and if the reaction is conducted in the presenceof water and neutralizing acid, quaternary ammonium group-containingresins may be formed.

In certain embodiments, the cationic resin is prepared byco-polymerization of a cationic monomer (e.g.,dimethyl-amino-propyl-methacrylate, dimethyl-amino-ethyl-methacrylate,dimethyl-amino-propyl-acrylamide or t-butyl-amino-ethyl-acrylate) withan acrylic or methacrylic ester monomer, or with styrene, or withacrylonitrile. In other embodiments, the cationic resin is prepared bythe reaction of amine-containing anhydride functional polymers with amono epoxide compound, for example as shown in U.S. Pat. No. 3,984,382,incorporated by reference herein.

In certain embodiments, the capped polyisocyanate curing agent is anisocyanate where the isocyanato groups have been reacted with a compoundso that the resultant capped isocyanate is stable to active hydrogens atroom temperature but reactive with active hydrogens at elevatedtemperature, usually between about 90° and about 200° C.

In certain embodiments, the polyisocyanate of the capped polyisocyanateis an aliphatic or an aromatic polyisocyanates, or mixtures thereof. Incertain embodiments, the capped polyisocyanate is an aliphaticpolyisocyanates, for example, trimethylene, tetramethylene,tetramethylxylylene, pentamethylene, hexamethylene, 1,2-propylene,1,2-burylens, 2,3-burylens, or 1,3-butylene diisocyanate. In certainembodiments, the polyisocyanate of the capped polyisocyanate is1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexane, or isophoronediisocyanate. In certain embodiments, the polyisocyanate of the cappedpolyisocyanate is an aromatic polyisocyanates, for example m-phenylene,p-phenylene, 4,4-diphenyl, 1,5-naphthalene or 1,4-naphthalenediisocyanate. In certain embodiments, the polyisocyanate of the cappedpolyisocyanate is diphenylmethane-4,4-diisocyanate (MDI) or polymericdiphenylmethane-4,4-diisocyanate (crude MDI). In certain embodiments,the polyisocyanate of the capped polyisocyanate is a mixedaliphatic-aromatic compound, such as 2,4- or 2,6-tolylene diisocyanate,or mixtures thereof, 4,4-toluidine diisocyanate, or 1,4-xylylenediisocyanate. In certain embodiments, the polyisocyanate of the cappedpolyisocyanate is as dianisidine diisocyanate, 4,4-diphenyletherdiisocyanate, chlorodiphenylene diisocyanate. In certain embodiments,the polyisocyanate of the capped polyisocyanate is a triisocyanate, suchas triphenylmethane-4,4,4-triisocyanate, 1,3,5-triisocyanatobenzene, or2,4,6-triisocyanatotoluene. In certain embodiments, the polyisocyanateof the capped polyisocyanate is a tetraisocyanate, such as4,4-dimethyldiphenylmethane-2,2,5,5-tetraisocyanate. In certainembodiments, the polyisocyanate of the capped polyisocyanate is apolymerized polyisocyanate, such as tolylene diisocyanate dimers ortrimers, and the like.

In certain embodiments, the polyisocyanate of the capped polyisocyanateis toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI),1,6-hexamethylene diisocyanate (HDI), phenyl isocyanate,4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI),meta-tetramethylxylene diisocyanate (TMXDI), nonanetriisocyanate (TTI)or vinyl isocyanate. In certain embodiments, the polyisocyanate of thecapped polyisocyanate is an isocyanurate, an allophanate, a biuret, or apolyurethane product derived from the above-mentioned isocyanates. Incertain embodiments, the polyisocyanate of the capped polyisocyanate isan addition products of a monomeric isocyanate with a polyester or apolyether polyol having terminal isocyanate groups.

In certain embodiments, the polyisocyanate of the capped polyisocyanateis a prepolymer derived from a polyol, for example polyether polyol orpolyester polyol, including polyols which are reacted with excesspolyisocyanates to form isocyanate-terminated prepolymers. These may besimple polyols such as glycols, for example, ethylene glycol andpropylene glycol, as well as other polyols such as glycerol,trimethylolpropane, hexanetriol, pentaerythritol, and the like, as wellas ether-alcohols such as diethylene glycol, tripropylene glycol and thelike and polyethers, that is, alkylene oxide condensates of the above.In certain embodiments, the alkylene oxides that may be condensed withthese polyols to form polyethers are ethylene oxide, propylene oxide,butylene oxide, styrene oxide and the like. These are generally calledhydroxy-terminated polyethers and can be linear or branched. In specificembodiments, the polyether is polyoxyethylene glycol having a molecularweight of approximately 1540, polyoxypropylene glycol having a molecularweight of approximately 1025, polyoxytetramethylene glycol,polyoxyhexamethylene glycol, polyoxynonamethylene glycol,polyoxydecamethylene glycol, polyoxydodecamethylene glycol, or a mixturethereof. In other embodiments, the polyether polyol is one derived fromreacting a polyol such as ethylene glycol, diethylene glycol,triethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol,1,6-hexanediol, or mixtures thereof; glycerol, trtmethylolethane,trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol,dipentaerythritol, tripentaerythritol, polypentaerythritol, sorbitol,methyl glucosides, sucrose, or the like; with an alkylene oxide, such asethylene oxide, propylene oxide, mixtures thereof, or the like.

In certain embodiments, the molecular weight of the polyol ranges fromabout 62 to about 1,000,000, or from about 62 to about 100,000, or fromabout 62 to about 10,000. In certain embodiments, the polyol has amolecule weight from about 300 to about 2000, for example when used insolvent borne high solids coatings. In certain embodiments, the polyolhas a the hydroxyl number from about 10 to about 1000. In certainembodiments, the polyol bears other functional groups, such as carboxyl,amino, urea, carbamate, amide and epoxy groups. In certain embodiment,the polyol is employed in a solvent free system, or as a solution in anorganic solvent, or as a dispersion/emulsion in water. In specificembodiments, the polyol is a polyether polyol, a polyester polyol, anacrylic polyol, an alkyd resin, or a polyurethane polyol.

In certain embodiments, the polyether polyol is a reaction product ofethylene or propylene oxide or tetrahydrofuran with a diol or a polyol.In certain embodiments, the polyether polyol is derived from a naturalproduct, such as cellulose and synthetic epoxy resins. In certainembodiments, the polyether polyol is a reaction product of a diol, atriol, or a polyol with a di- or polybasic acid. In certain embodiments,the alkyd resin is prepared in a similar process except that monofunctional fatty acids may be included. In certain embodiments, theacrylic polyol is a reaction product of an ester of acrylic ormethacrylic acid with an hydroxyl containing monomer, such ashydroxyethyl, hydroxypropyl or hydroxybutyl ester of acrylic ormethacrylic acid. These acrylic polymers can also contain other vinylmonomers such as styrene or acrylonitrile vinyl chloride. In certainembodiments, the polyurethane polyol is the reaction product of apolyether or polyester polyol with a diisocyanates.

Such polyols may be prepared in bulk in the absence of a solvent or inthe presence of a diluent or by emulsion polymerization in water.Alternatively, they may be prepared in bulk or in a solvent and thendispersed in water. For a description of the methods of preparingpolyols see Organic Coatings Science Technology, vol. 1,Wiley-Interscience Co., 1992.

In certain embodiments, the capped polyisocyanate is capped with aremovable blocking group. In various embodiments, the blocking group isa malonate, a triazole, an ε-caprolactam, a phenol, a ketoxime, apyrazole, an alcohol, a glycol, a glycol ether, or a uretdione. Incertain embodiments, de-blocking to the isocyanate is a displacementreaction, wherein the blocking group is displaced with another group.

In certain embodiments, the capping agent of the capped isocyanate is analcohol, for example a glycol monoether or an amino alcohol. In certainembodiments, the capping agent is an aliphatic alcohols (e.g., methanolor 2-ethylhexyl alcohol), a cycloaliphatic alcohol (e.g., cyclohexanol),an aromatic alkyl alcohols (e.g., benzyl alcohol), a glycol monoether(e.g., a monoalkyl ether of ethylene glycol, such as the monobutyl etherof ethylene glycol), an amino alcohols (e.g., dimethylethanolamine.), anoximes (e.g., methyl ethyl ketoxime), a lactam (e.g.,epsilon-caprolactam), an aliphatic amine (e.g., dibutylamine), or abeta-dicarbonyl compound (e.g., acetyl acetone).

In certain embodiments, the capped polyisocyanate is fully capped, thatis, no free isocyanate groups remain. In other embodiments, the cappedpolyisocyanate is partially capped, for example, half-cappeddiisocyanate. In such embodiments, the partially capped isocyanate canthen be reacted with a portion of the active hydrogen groups, i.e.,hydroxyl groups, under conditions which will not uncap the cappedisocyanate group. This reaction in effect fully caps the isocyanatemaking it a part of the resin molecule, providing a one-componentsystem. In such embodiments, the reaction of the partially cappedpolyisocyanate and the active hydrogen functionality in the resin isconducted at low or moderate temperature, for example less than about150° C., to preserve the capped isocyanate groups in order to avoidgelation and to retain latent crosslinking sites. Solvent, particularlya water-miscible one such as an ether, ester or ketone, may be used. Incertain embodiments, whether partially capped or fully capped, theelectrocoating composition comprises about 0.1 to about 1.0 cappedisocyanate groups for each active hydrogen.

In certain embodiments, the capped polyisocyanate is formed by reactinga carbonate (such as ethylene or propylene carbonate) with a polyamine.

In certain embodiments, the electrocoating composition comprises activehydrogen-containing ionic resin in an amount from about 20 to about 90percent, for example from about 30 to about 70 percent by weight basedon the weight of resin solids present. In certain embodiments, theelectrocoating composition comprises capped polyisocyanate in an amountfrom about 5 to about 75 percent, for example from about 20 to about 60percent by weight based on the weight of resin solids present.

In certain embodiments, the electrocoating composition is an aqueousdispersions. The term “dispersion” refers to a two-phase transparent,translucent or opaque resinous system in which the resin is in thedispersed phase and the water is in the continuous phase. In certainembodiments, the average particle size of the resinous phase is lessthan 10 microns, for example less than about 5 microns, or less thanabout 0.5 microns. In certain embodiments, the concentration of theresinous phase in the aqueous medium is at least about 1 percent, forexample from about 2 to about 60 percent by weight based on weight ofthe aqueous dispersion. In certain embodiments, the electrocoatingcomposition is in the form of a resin concentrate, they having a resinsolids content of about 25 to about 60 percent by weight based on theweight of the aqueous dispersion. In certain embodiments, theelectrocoating composition comprises resin solids content of about 5 toabout 25 percent by weight based on total weight of the electrocoatingcomposition.

In certain embodiments, the aqueous electrocoating composition furthercomprises a coalescing solvent. In certain embodiments, the coalescingsolvent is a hydrocarbon, an alcohol, an ester, an ether, or a ketone.In certain embodiments, the coalescing solvent is isopropanol, butanol,2-ethylhexanol, isophorone, 4-methoxy-pentanone, ethylene or propyleneglycol, or a monoethyl, monobutyl a monohexyl ethers of ethylene glycol.In certain embodiments, the coalescing solvent is present in an amountfrom about 0.01 to about 25 percent, for example from about 0.05 toabout 5 percent by weight based on the weight of the electrocoatingcomposition.

In certain embodiments, the aqueous electrocoating composition furthercomprises an alcohol or a polyol solubilized or dispersed in water inthe presence of nonionic groups or a nonionic surfactant. In certainembodiments, the alcohol or polyol is incorporated in the bisphenolepoxy resin itself, for example, a bisphenol epoxy resin reacted with amethoxy-polyethylene glycol or a methoxy-polyethylene-ether-amine with amolecular weight of from about 500 to about 2000.

In certain embodiments, the aqueous electrocoating composition furthercomprises a nonionic surfactant. An epoxy or an acrylic or polyesterresin may be dispersed in water. The nonionic groups can be a part ofthe resin structure or a part of an external surfactant. In a specificembodiment, the aqueous electrocoating composition further comprises asolid bisphenol A glycidyl resin with a molecular weight of from about900 to about 4000.

In certain embodiments, the vehicle resin is neutralized to impart watersolubility or dispersibility, for example when the resin is a cationicresin, by neutralizing the resin with a water-soluble organic acid, suchas formic acid, acetic acid, lactic acid or the like to impart watersolubility or dispersibility and, when the resin is an anionic resin, byneutralizing the resin with an alkali such as amine, alkali metalhydroxide or the like to impart water solubility or dispersibility.

In certain embodiments, the cationic resin is dispersed in water in thepresence of a water soluble organic acid or inorganic acid. In certainembodiments, the water soluble organic acid is formic acid, acetic acid,glycolic acid, or lactic acid. In certain embodiments, the water solubleinorganic acid is sulfamic acid.

In certain embodiments, the electrocoating composition further comprisesordinary additives for coatings, such as coloring pigments (e.g.,titanium white, carbon black, red iron oxide, chrome yellow, or thelike); extender pigments (e.g., talc, calcium carbonate, mica, clay,silica, or the like); and/or rust-preventive pigments (e.g., a chromepigment such as strontium chromate, a lead pigment such as basic leadsilicate or lead chromate, or the like)

In certain embodiments, the electrocoating composition further comprisesa pigment composition and/or various additives such as surfactants,wetting agents or additional catalysts. The pigment composition may beof the conventional types comprising, for example, iron oxides, leadoxides, strontium chromate, carbon black, coal dust, titanium dioxide,talc, barium sulfate, as well as color pigments such as cadmium yellow,cadmium red, chromium yellow and the like. The pigment content of thedispersion is usually expressed as a pigment-to-resin ratio. In certainembodiments, the pigment-to-resin ratio is within the range of about0.02:1 to about 1:1. In certain embodiments, the other additivesdescribed above are present in amounts of about 0.01 to about 3 percentby weight based on the total solids weight of resins present.

In certain embodiments, the electrocoating composition is prepared byblending and dispersing the capped polyisocyanate crosslinker, theactive hydrogen-containing ionic resin, and the catalyst describedherein, in water. If pigments are added they can be dispersed separatelyin the resin. If neutralization of the ionic resin with an acid isrequired, the acid can be added to the resin or to the water phase. Incertain embodiments, high shear dispersers are used to emulsify ordisperse the resin.

In certain embodiments, the electrocoating formulation comprises thecapped polyisocyanate in an amount sufficient to facilitatecrosslinking. In certain embodiments, the electrocoating compositioncomprises the catalyst described herein in an amount from about 0.01 toabout 5 weight percent, for example from about 0.1 to about 1.0 weightpercent, of metal based on the total resin solids in the formulation.

In certain embodiments, the electrocoating composition is used bycontacting the coating composition with an electrically conductive anodeand an electrically conductive cathode, where the surface to be coatedis either the cathode or the anode, depending on whether the ionicactive hydrogen-containing resin is anionic or cationic. Followingcontact with the coating composition, an adherent film is deposited onone electrode when a sufficient voltage is impressed between theelectrodes. The conditions under which electrodeposition is carried outare, in general, similar to those used in electrodeposition of othertypes of coatings. In certain embodiments, the applied voltage is fromabout 1 volt to about 3000 volts, for example from about 50 to about 500volts. In certain embodiments, the current density is between about 0.5and about 5 amperes per square foot, tends to decrease duringelectrodeposition indicating the formation of an insulating film. Thecoating compositions of the present invention can be applied to avariety of electroconductive substrates especially metals such as steel,aluminum, copper, magnesium and conductive carbon coated materials.

Thus, in related embodiments, provided herein is a method ofelectrocoating a substrate comprising contacting the coating compositionwith an electrically conductive anode and an electrically conductivecathode, where the surface to be coated is either the cathode or theanode, depending on whether the ionic active hydrogen-containing resinis anionic or cationic, and applying a voltage between the electrodes.The components of the electrocoating composition, as well as theconditions of the method, are described in more detail hereinabove.

In certain embodiments, the electrocoating composition produces a curedfilm with a thickness from about 10 to about 40 μm. In certainembodiments, after the coating has been applied by electrodeposition, itis cured, for example by baking at elevated temperatures, for examplefrom about 90° to about 260° C., for example for about 1 to about 40minutes.

4.4 Corrosion Inhibiting Compositions and Uses Thereof

In certain embodiments, the catalysts described herein are used ascorrosion inhibitors in coating compositions for metallic surfaces.Thus, provided herein are coating compositions for metallic surfacescomprising a catalyst compositions comprising a metal amidine complexand one or more second compounds, as described herein. In certainembodiments, a corrosion inhibiting coating composition is a coatingmaterial, for example an aqueous coating material. In certainembodiments, the corrosion inhibiting coating composition is a lacquer,a paint, or a varnish. In certain embodiments, the corrosion inhibitingcoating composition comprises an organic film-forming binder.

In certain embodiments, the catalyst composition is present in thecorrosion inhibiting composition in an amount from about 0.05 to about10 wt. %, about 0.1 to about 10 wt. %, about 0.5 to about 10 wt. %,about 1 to about 10 wt. %, about 2 to about 8 wt. %, about 2 to about 6wt. %, about 2 to about 4 wt. %, or about 4 to about 8 wt. %, based onthe total weight of the coating composition.

In certain embodiments, the metal amidine complex and the secondcompound are of the catalyst composition are, respectively:Zn(1-methylimidazole)₂(acetate)₂ and DABCO;Zn(1-methylimidazole)₂(acetate)₂ and zinc acetylacetonate;Zn(1-methylimidazole)₂(acetate)₂ and dibutyltin dilaurate;Zn(1-methylimidazole)₂(acetate)₂ and zirconium acetylacetonate;Zn(1-Methylimidazole)₂(2-Ethylhexanoate)₂ and a bismuth carboxylate;Zn(1,1,3,3-Tetramethylguanidine)₂(2-Ethylhexanoate)₂ and a bismuthcarboxylate; Zn(1-methylimidazole)₂(acetate)₂ and a bismuth carboxylate;Zn(1-methylimidazole)₂(acetate)₂ and lithium neodecanoate;Zn(2-Ethylhexanoate)₂(acetate)₂ and phenylmercuric acetate;Zn(1-methylimidazole)₂(acetate)₂ and dinonylnaphthalene disulfonate;Zn(1-methylimidazole)₂(acetate)₂ and 1,2-dimethylimidazole; orZn(1-methylimidazole)₂(acetate)₂ and 2-methylimidazole.

In certain embodiments, the organic film-forming binder is an epoxyresin, a polyurethane resin, an amino resin, an acrylic resin, anacrylic copolymer resin, a polyvinyl resin, a phenolic resin, astyrene/butadiene copolymer resin, a vinyl/acrylic copolymer resin, apolyester resin, an alkyd resin, or a mixture of two or more of theseresins, or an aqueous basic or acidic dispersion of one or more of theseresins, or an aqueous emulsion of one or more of these resins.

In certain embodiments, the organic film-forming binder is an alkydresin, an acrylic resin, a two-component epoxy resin, a polyurethaneresin, a polyester resin (which may be saturated or unsaturated), awater-dilutable phenolic resin (a dispersion derived thereof), awater-dilutable urea resin, a resin based on one or more vinyl/acryliccopolymers, or a hybrid systems based on, for example, one or more epoxyacrylate. In certain embodiments, these organic film-forming binders areuseful for aqueous coating compositions.

In particular embodiments, the alkyd resin is a water-dilutable alkydresin system which can be employed in air-drying form or in the form ofstoving systems, optionally in combination with water-dilutable melamineresins; the systems may also be oxidatively drying, air-drying orstoving systems which are optionally employed in combination withaqueous dispersions based on acrylic resins or copolymers thereof, with,for example vinyl acetates.

In certain embodiments, the organic film-forming binder is an acrylicresin, which is a pure acrylic resin, an epoxy acrylate hybrid system,an acrylic acid or acrylic ester copolymer, a combination with a vinylresin, or a copolymer with a vinyl monomer such as vinyl acetate,styrene, or butadiene. In certain embodiments, these acrylic resins areuseful for systems that can be air-drying systems or stoving systems.

In certain embodiments, the organic film-forming binder is awater-dilutable epoxy resins in combination with a polyaminecrosslinker. In certain embodiments, where a liquid epoxy resins areused, the addition of organic solvents to aqueous systems can beomitted. In certain embodiments where solid resins or solid-resindispersions are used, small amounts of solvent may be added in order toimprove film formation.

In certain embodiments, the organic film-forming binder is an epoxyresin. In certain embodiments, the epoxy resin is one based on anaromatic polyol, for example one based on a bisphenol. In certainembodiments, the epoxy resin is employed in combination with acrosslinker, for example an amino- or hydroxy-functional compounds, anacid, an acid anhydride, or a Lewis acid. In certain embodiments, thecrosslinker is a polyamine, a polyaminoamide, a polysulfide-basedpolymer, a polyphenol, boron fluoride or its complex compounds, apolycarboxylic acid, a 1,2-dicarboxylic anhydride, or a pyromelliticdianhydride.

In certain embodiments, the organic film-forming binder is apolyurethane resin. In certain embodiments, the polyurethane resin isderived from a polyether, a polyester, and/or a polybutadiene withterminal hydroxyl groups, on the one hand, and from an aliphatic oraromatic polyisocyanate on the other hand.

In certain embodiments, the organic film-forming binder is a polyvinylresin. In certain embodiments, the polyvinyl resin is apolyvinylbutyral, a polyvinyl acetate, or a copolymer thereof.

In certain embodiments, the organic film-forming binder is a phenolicresin. In certain embodiments, the phenolic resin is a synthetic resinin the course of whose construction phenols are the principal component.In specific embodiments, the phonelic resin is a phenol-, cresol-,xylenol- or resorcinol-formaldehyde resin, an alkylphenolic resin, or acondensation product of one or more phenols with acetaldehyde, furfurol,acrolein or other aldehydes.

In certain embodiments, the corrosion inhibiting coating compositionsfurther comprises one or more of the following: pigment, dye, filler,flow control agent, dispersant, thixotropic agent, adhesion promoter,antioxidant, light stabilizer, and curing catalyst. In certainembodiments, such optional additional ingredients include other knownanticorrosion agents, for example anticorrosion pigments, such asphosphate- or borate-containing pigments or metal oxide pigments orother organic or inorganic corrosion inhibitors, for example salts ofnitroisophthalic acid, phosphoric esters, technical-grade amines orsubstituted benzotriazoles.

In certain embodiments, the pigment is titanium dioxide, iron oxide,aluminum bronze, or phthalocyanine blue.

In certain embodiments, the filler is talc, alumina, aluminum silicate,barytes, mica, or silica. In certain embodiments, the corrosioninhibitors is applied to a support material, such as, for example, apulverulent fillers or pigment.

In certain embodiments, the flow control agent is based on a modifiedbentonite. In certain embodiments, the thixotropic agent is based on amodified bentonite.

In certain embodiments, the adhesion promoter is based on a modifiedsilane.

In certain embodiments, the corrosion inhibiting coating compositionfurther comprises both a basic filler and a pigment. Such a combinationmay give rise to a synergistic effect on corrosion inhibition. Inparticular embodiments, the basic filler/pigment is calcium carbonate ormagnesium carbonate, zinc oxide, zinc carbonate, zinc phosphate,magnesium oxide, alumina, aluminum phosphate, or mixtures thereof. Incertain embodiments, the basic organic pigment is based onaminoanthraquinone.

In certain embodiments, the corrosion inhibiting coating composition isprepared by adding the corrosion inhibiting composition (i.e., thecatalysts described herein) to the coating material during itspreparation, for example during pigment dispersion by grinding, or bydissolving the corrosion inhibiting compound in a solvent and thestirring the solution into the coating composition. In certainembodiments, the solution of corrosion inhibiting compound, for examplean aqueous solution of the corrosion inhibiting compound, is used forpretreating the metal surface, which can then be subsequently coatedwith a topcoat.

In certain embodiments, the corrosion inhibiting compound is useddirectly in the preparation of the organic film-forming binder byaddition polymerization or condensation polymerization of monomers. Insuch embodiments, the corrosion inhibitors is mixed in solid form, ordissolved, with the monomers prior to the polymerization reaction.

In certain embodiments, the corrosion inhibiting coating composition isapplied to a substrate customary techniques, for example by spraying,dipping, spreading or electrodeposition. In certain embodiments, aplurality of coats are applied. The corrosion inhibitors are addedprimarily to the base layer (primer), since they are active inparticular at the metal-coating interface. However, they can also beadded to the intermediate coat or topcoat, as well. Depending on whetherthe binder is a physically, chemically or oxidatively drying resin or aheat-curing or radiation-curing resin, the coating is cured at roomtemperature or by heating (stoving) or by irradiation.

In certain embodiments, the corrosion inhibiting coating composition isa primer for metallic substrates such as, for example, iron, steel,copper, zinc or aluminum, or alloys thereof.

In certain embodiments, the corrosion inhibiting compound impartsadhesion properties between the coating and the substrate (e.g., ametal), showing no adverse effects on the storage stability of the novelcoating compositions, and exhibit good compatibility with the binder.

In certain embodiments is provided a process for protecting a corrodablemetal substrate, comprising applying thereto a corrosion inhibitingcoating composition comprising an organic film-forming binder and atleast one catalyst described herein (as corrosion inhibitor), andsubsequently drying and/or curing the coated metal substrate.

In certain embodiments is provided a process for preparing acorrosion-resistant surface on a corrodable metal substrate, comprisingtreating surface of the corrodible metal substrate with a corrosioninhibiting coating composition comprising an organic film-forming binderand at least one catalyst described herein (as corrosion inhibitor), andsubsequently drying and/or curing the treated corrodible metalsubstrate.

4.5 Examples

Metal Amidine Complex Preparation

[Metal(Amidine)₂(Ligand)_(x)] of this invention: To a mixture of amidine(2.0 moles) and metal carboxylate, or acetylacetonate (1 mole) was addedmethanol to make a 50% solution. The mixture was held at 50° C. for 2hours or until it became a clear solution. The solution was filtered anddried. The example catalysts of Metal(Amidine)₂(Ligand)_(x) are listedin the TABLE below. x is the oxidation state of the metal.

Example Catalyst Physical Form  1 Zn(DBN*)₂(acetate)₂ white powder  2Zn(DBN*)₂(formate)₂ white powder  3 Zn(DBN*)₂(2-ethylhexanoate)₂ clearliquid  4 Zn(DBU*)₂(acetate)₂ white powder  5 Zn(DBU*)₂(formate)₂ whitepowder  6 Zn(DBU*)₂(2-ethylhexanoate)₂ clear liquid  7Zn(1-methylimidazole)₂(acetate)₂ white powder  8Zn(1-methylimidazole)₂(formate)₂ white powder  9Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ clear liquid 10Zn(1,2-dimethylimidazole)₂(acetate)₂ white powder 11Zn(1,2-dimethylimidazole)₂(formate)₂ white powder 12Zn(1,2-dimethylimidazole)₂(2-ethylhexanoate)₂ clear liquid 13Zn(1-butylimidazole)₂(acetate)₂ white powder 14Zn(1-butylimidazole)₂(formate)₂ white powder 15Zn(1-butylimidazole)₂(2-ethylhexanoate)₂ clear liquid 16Zn(imidazole)₂(acetate)₂ white powder 17 Zn(imidazole)₂(formate)₂ whitepowder 18 Zn(imidazole)₂(2-ethylhexanoate)₂ clear liquid 19Zn(tetramethylguanidine)₂(acetate)₂ white powder 20Zn(tetramethylguanidine)₂(formate)₂ white powder 21Zn(tetramethylguanidine)₂(2-ethylhexanoate)₂ clear liquid 22Zn(1,3-diphenylguanidine)₂(acetate)₂ white powder 23Zn(1,3-diphenylguanidine)₂(formate)₂ white powder 24Zn(1,3-diphenylguanidine)₂(2-ethylhexanoate)2 clear liquid 25Zn(4,4-dimethyl-2-imidazoline)₂(acetate)₂ white powder 26Zn(4,4-dimethyl-2-imidazoline)₂(formate)₂ white powder 27Zn(4,4-dimethyl-2-imidazoline)₂(2- clear liquid ethylhexanoate)₂ 28Zn(MACKAZOLINE T*)₂(acetate)₂ brown liquid 29 Zn(MACKAZOLINET*)₂(formate)₂ brown liquid 30 Zn(MACKAZOLINE T*)₂(2-ethylhexanoate)2brown liquid 31 Zn(Lindax-1*)₂(acetate)₂ brown liquid 32Zn(Lindax-1*)₂(formate)₂ brown liquid 33Zn(Lindax-1*)₂(2-ethylhexanoate)₂ brown liquid 34Zn(1-methylimidazole)₂(acac)₂ white powder 35Bi(1-methylimidazole)₂(acetate)₃ white powder 36Ca(1-methylimidazole)₂(acetate)₂ white powder 37Cd(1-methylimidazole)₂(acetate)₂ white powder 38La(1-methylimidazole)₂(acetate)₃ white powder 39Zr(1-methylimidazole)₂(acetate)_(x)(hydroxide)_(y) white powder x + y =4 40 Sn(1-methylimidazole)₂(2-ethylhexanoate)₂ brown liquid 41Hf(1-methylimidazole)₂(acac)₄ yellow liquid *DBN:1,5-Diazabicyclo[4.3.0]non-5-ene DBU: 1,8-Diazabicyclo[5.4.0]undec-7-eneAmidines, Zinc Acetate Anhydrous, and Zinc Acetylacetonate [Zn(acac)₂]supplied by Aldrich. Zinc Formate Anhydrous and Zinc 2-Ethylhexanoatesupplied by Alfa Aesar. MACKAZOLINE T supplied by McIntyre Group is talloil hydroxyethyl imidazoline. Lindax-1 supplied by Lindau Chemicals Inc.is 1-(2-hydroxypropyl)imidazole

Reference is made to Example 1-31 of U.S. Pat. No. 7,485,729, herebyspecifically incorporated by reference herein, which sets forth variousspecific examples of coating preparations, analogous to those describedherein without the second compound included in the catalyst composition.

The following examples are illustrative of the scope of the disclosure,but are non-limiting.

Examples 1-3

Coating Preparation: Cathodic electrocoat baths were prepared by mixingDI water and main vehicle emulsions listed in TABLE 1. Main vehicleemulsions were as prepared based on Examples I-A of U.S. Pat. No.5,767,191 (S. R. Zawacky et. Al., PPG), respectively.Zn(DBU)2(Carboxylate)2, Bismuth Carboxylate, and a mixture ofZn(DBU)2(Carboxylate)2 and Bismuth Carboxylate were incorporated intothe main vehicle prior to emulsification at a concentration of 1.5%catalyst based on total resin solids. Electrocoats were deposited onpretreated cold rolled steel panels at a dry film thickness ofapproximately 20 μm and baked at the peak metal temperatures (PMT) of177° C. and 163° C. for 20 minutes.

Liquid coating compositions for Examples 1-3 (amounts in % by weight):

TABLE 1 Examples 1 2 3 DI Water 51.84 51.84 51.84 Main Vehicle Emulsionwith 1.5% of a 48.16 0 0 Zn(DBU)₂(Carboxylate)₂ Based on Total ResinSolids (35.0% Solids) Main Vehicle Emulsion with 1.5% a 0 48.16 0Bismuth Carboxylate Based on Total Resin Solids (35.0% Solids) MainVehicle Emulsion with 1.5% of 0 0 48.16 a Mixture of 50% aZn(DBU)₂(Carboxylate)₂ and 50% a Bismuth Carboxylate Based on TotalResin Solids (35.0% Solids)

TABLE 2 Examples Bake Schedule MEK Double Rubs 1 177° C.(PMT) × 20′ 100(slight mar) 1 163° C.(PMT) × 20′ 100 (slight mar) 2 177° C.(PMT) × 20′100 (slight mar) 2 163° C.(PMT) × 20′ 100 (slight mar) 3 177° C.(PMT) ×20′ 100 (no mar) 3 163° C.(PMT) × 20′ 100 (no mar)

Examples 1-3 demonstrate that a mixture of 50% of aZn(DBU)₂(Carboxylate)₂ and 50% of a bismuth carboxylate based on weightis an effective catalyst for cathodic electrocoat and the synergeticeffects of the mixture. Even at distinctly lower baking temperatures,completely crosslinked coatings were obtained with the liquid coatingcomposition according to the disclosure. These results indicate thatsuch a synergistic effect would be observed with any metal carboxylateas the second compound.

Examples 4-5

Coating Preparation: 2-component solventborne polyurethane clearcoatswere by Part A of polyol component and Part B of isocyanate componentlisted in TABLE 3. A mixture of 50% of aZn(1,1,3,3-Tetramethylguanidine)₂(Carboxylate)₂ and 50% zinc octoatebased on weight was incorporated into Part A of polyol component priorto mix with Part B of isocyanate component. Films were casted onpretreated cold rolled steel panels using a #50 drawdown rod to yield adry film thickness of approximately 50 μm. One set of panels was curedat 80° C. for 30 minutes and another set was allowed to cure for 7 daysat room temperature (Air dried).

Liquid coating compositions for Examples 4-5 (amounts in % by weight):

TABLE 3 Examples 4 5 Part A: Joncryl 500 (Polyol Component) 60.26 60.26BYK 310 (Silicone Flow Agent; 0.955 0.955 20% in methyl amyl ketone)Methyl Amyl ketone (Solvent) 15.02 15.02 AZn(1,1,3,3-Tetramethylguanidine)₂ 0.025 0 Carboxylate A mixture of 50% aZn(1,1,3,3- 0 0.025 Tetramethylguanidine)₂(Carboxylate)₂ and 50% ZincOctoate Part B: Desmodur XP-2410 (Isocyanate Component) 22.14 22.14Methyl Amyl ketone (Solvent) 1.60 1.60 Total 100.00 100.00

TABLE 4 Examples 4 5 Pendulum Hardness Pendulum Hardness Film: Baked at80° C. × 30′ 8 28 Post Cure: 1 day 20 45 Post Cure: 3 days 60 73 PostCure: 7 days 61 73 Film: Air Dried Post Cure: 1 day 8 18 Post Cure: 3days 47 57 Post Cure: 7 days 48 60

Examples 4-5 demonstrate that a mixture of 50% of aZn(1,1,3,3-Tetramethylguanidine)₂(Carboxylate)₂ and 50% zinc octoatebased on weight is an effective catalyst for 2-component solventbornepolyurethane clearcoats and the synergistic effects of the mixture forboth baked and air dried systems. Completely crosslinked coatings wereobtained with the liquid coating composition according to thedisclosure. These results would indicate that such a synergistic effectwould be observed with any metal carboxylate as a second compound.

Examples 6-7

Coating Preparation: Desmophen 651 MPA polyester polyol and Trixene BI7984 MEKO blocked HDI polyisocyanate were homogeneously mixed. The resinmixtures were catalyzed with metal catalysts listed in TABLE 5 at aconcentration of 0.14% metal catalyst based on the total resin used.Films were cast on pretreated steel panels at a dry film thickness ofapproximately 25 μm and baked for 30 minutes at 135° C.

Liquid coating compositions for Examples 6-7 (amounts in % by weight):

TABLE 5 Examples 6 7 Desmophen 651MPA (Polyester Polyol) 36.59 36.59Trixene BI 7984 (Blocked Polyisocyanate) 44.19 44.19 BYK 310 (SiliconeFlow Agent) 0.15 0.15 Methyl Isobutyl Ketone (Solvent) 6.31 6.31 PMAcetate (Solvent) 6.31 6.31 Xylene (Solvent) 6.31 6.31 AZn(1,1,3,3-Tetramethylguanidine)₂(Carboxylate)₂ 0.14 0 A mixture of a50% Zn(1,1,3,3-Tetramethyl- 0 0.14 guanidine)₂(Carboxylate)₂ and 50%Zinc Octoate Total 100.00 100.00

TABLE 6 Examples Bake Schedule Pendulum Hardness MEK Double Rubs 6 135°C. × 30′ 160 98 7 135° C. × 30′ 165 100+

Examples 6-7 demonstrate that a mixture of 50% aZn(1,1,3,3-Tetramethylguanidine)₂(Carboxylate)₂ and 50% zinc octoatebased on weight is an effective catalyst for MEKO blocked HDIpolyisocyanate liquid coatings and the synergetic effects of themixture. Even at distinctly lower baking temperatures, completelycrosslinked coatings were obtained with the liquid coating compositionaccording to the invention. These results would indicate that such asynergetic effect would be observed with any metal carboxylate as asecond compound.

Examples 8-14

A clear millbase (Part A), containing the acrylic polyol is preparedusing the following ingredients:

Ingredients - Polyol Part A Weight Joncryl 500 - Acrylic Polyol 66.96Xylene 3.89 EEP 8.94 MIBK 6.61 Premix next 4 Items MIBK 6.40 ButylAcetate 2.80 Tinuvin 292 0.73 Tinuvin 1130 1.47 Byk 310 0.18 MIBK 1.0Total weight of clear base 98.98

An isocyanate curing agent solution (Part B) is prepared using thefollowing ingredients:

Curing Agent solution IsocyanatePartB Weight Xylene 6.89 Butyl Acetate9.97 EEP (Ethyl 3-Ethoxypropionate). 2.01 MIBK(Methyl Isobutyl Ketone)9.37 Basonat HI 100 - HDI Trimer 37.46 Total weight of Part B 65.70

The print resistance of various coatings was measured using the ASTM D2091-96 test method. After the requisite cure (30′@ 600 C), a 1.5×1.25″piece of metal mesh is placed on the surface of the panel with 2000grams weight on top of it for 20 seconds. The weight is then removed andthe surface of the coating was examined for mesh profile, which is ameasure of sufficient cure. If no mesh profile is seen on the cured filmthen the coating is considered to be sufficiently cured.

Various coating compositions containing a zinc amidine carboxylatecatalyst either alone or in combination with a carboxylic acid secondcompound were prepared using the formulations described below, and printresistance was measured using the protocol described above.

Examples 8 9 10 11 12 13 14 Joncryl 500 Clear Millbase 98.98 98.98 98.9898.98 98.98 98.98 98.98 Catalyst Systems EvaluatedZn(1-MI)₂(2-ethylhexanoate)₂ 0.13 0.13 0.13 0.13 0.13 0.13 0.13Cyclohexane Dicarboxylic 0.00 1.14 0.00 0.00 0.00 0.00 0.00 NeodecanoicAcid 0.00 0.00 2.27 0.00 0.00 0.00 0.00 NEO 913 Acid(a blend of 0.000.00 0.00 2.55 0.00 0.00 0.00 branchedC9 and C13 acids Neo HeptanoicAcid 0.00 0.00 0.00 0.00 1.72 0.00 0.00 Neo Pentanoic Acid 0.00 0.000.00 0.00 0.00 1.35 0.00 Butyl Octanoic acid 0.00 0.00 0.00 0.00 0.000.00 2.64 Total Weight of Part A 99.11 100.25 101.38 101.66 100.83100.46 101.75 Weight of Activator - Part B 65.70 65.70 65.70 65.70 65.7065.70 65.70 NCO:OH 1.5:1.0 1.5:1.0 1.5:1.0 1.5:1.0 1.5:1.0 1.5:1.01.47:1.0 Cure schedule 30 Mins @ 60° C. ADFT - Mils 1.55 1.20 1.35 1.351.40 1.32 1.45 Print Test - Time out of oven   0 Hours Print No No No NoNo No Print Print Print Print Print Print 0.5 Hours Print 1.0 HoursPrint 1.5 Hours Print 2.0 Hours Print 2.5 Hours Print 3.0 Hours Print4.0 Hours Print 5.0 Hours Print

The above results show that coating compositions comprising carboxylicacids as a second compound in combination with a zinc amidinecarboxylate catalyst result in a faster cure compared a correspondingcoating composition without a carboxylic acid as a second compound.

The examples set forth above are provided to give those of ordinaryskill in the art with a complete disclosure and description of how tomake and use the claimed embodiments, and are not intended to limit thescope of what is disclosed herein. Modifications that are obvious topersons of skill in the art are intended to be within the scope of thefollowing claims. All publications, patents, and patent applicationscited in this specification are incorporated herein by reference as ifeach such publication, patent or patent application were specificallyand individually indicated to be incorporated herein by reference.

Illustrative embodiments:

1. A composition comprising a metal amidine complex and a secondcompound, wherein the second compound is a metal carboxylate or acarboxylic acid.

2. The composition of item 1, wherein the metal amidine complex is ofthe chemical formula M(amidine)_(w)(carboxylate)₂, wherein w is aninteger from 1 to 4.

3. The composition of item 1 or 2, wherein the metal of the metalamidine complex is zinc, lithium, sodium, magnesium, barium, potassium,calcium, bismuth, cadmium, aluminum, zirconium, tin, hafnium, titanium,lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten,or cesium.

4. The composition of item 1 or 3, wherein the amidine of the metalamidine complex is an amidine of formulae I-VIII as set forth anddefined in paragraphs [0030]-[0035].

5. The composition of any of items 1-4, wherein the carboxylate is ofthe following formula:

as set forth and defined in paragraph [0037].

6. The composition of any one of items 1-5, wherein the second compoundis a compound set forth in the tables in paragraph [0043].

7. The composition of any one of items 1-6, wherein the second compoundis a zinc carboxylate.

8. The composition of any one of items 1-6, wherein the second compoundis a bismuth carboxylate.

9. The composition of any one of items 1-6, wherein the second compoundis a carboxylic acid.

10. A coating composition comprising:

-   -   (a) a binder having uretdione groups and optionally isocyanate        groups; and    -   (b) the composition of any one of items 1-9.

11. The coating composition of item 10, further comprising:

-   -   (c) an acid scavenger.

12. A coating composition comprising:

-   -   (a) an epoxy compound;    -   (b) a carboxyl, an anhydride, a dicyandiamide (DICY), or a        phenolic compound; and    -   (c) the composition of any one of items 1-9.

13. A coating composition comprising:

-   -   (a) a bisphenol A epoxy/amino resin with an equivalent weight of        from about 200 to about 2000;    -   (b) an aromatic or aliphatic isocyanate with a removable        blocking group; and    -   (c) the composition of any one of items 1-9.

14. A coating composition comprising:

-   -   (a) an organic film-forming binder; and    -   (b) the composition of any one of items 1-9.

15. An electrocoating composition comprising:

-   -   (a) a cationic resin;    -   (b) a capped polyisocyanate; and    -   (c) the composition of any one of items 1-9.

16. The electrocoating composition of item 15, wherein the cationicresin is an epoxy-amine reaction product of a bisphenol A epoxy resinwith an epoxy equivalent weight of between 200 and 2000 and a primaryamine, a secondary amine, or a tertiary amine.

17. A polyurethane coating composition comprising:

-   -   (a) a polyol;    -   (b) a polyisocyanate; and    -   (c) the composition of any one of items 1-9.

18. A coating composition comprising:

-   -   (a) a binder;    -   (b) a hardener; and    -   (c) the composition of any one of items 1-9.

19. The coating composition of item 18, wherein the hardener is anaromatic or aliphatic isocyanate and wherein the isocyanate contains aremovable blocking group.

We claim:
 1. A catalyst composition comprising a metal amidine complexand a second compound, wherein the second compound is a metalcarboxylate or a carboxylic acid, wherein the metal of the metal amidinecomplex and the metal of the metal carboxylate are not identical.
 2. Thecatalyst composition of claim 1, wherein the metal amidine complex is ofthe chemical formula metal(amidine)_(w)(carboxylate)₂, wherein w is aninteger from 1 to
 4. 3. The catalyst composition of claim 1, wherein themetal of the metal amidine complex and the metal of the metalcarboxylate are independently zinc, lithium, sodium, magnesium, barium,potassium, calcium, bismuth, cadmium, aluminum, zirconium, tin, hafnium,titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum,tungsten, or cesium.
 4. The catalyst composition of claim 1, wherein theamidine of the metal amidine complex is an amidine of one of formulaeI-VIII:

wherein R¹ is hydrogen, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl, an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms; R² and R³ are eachindependently hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, or C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl, or R² and R³ are joinedto one another by an N═C—N linkage to form a heterocyclic ring with oneor more hetero atoms or a fused bicyclic ring with one or moreheteroatoms; R⁴ is hydrogen, C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or ahydroxyl group which can be optionally etherified with a hydrocarbylgroup having up to 8 carbon atoms; R⁵, R⁶, R⁷, and R⁸ are independentlyhydrogen, alkyl, substituted alkyl, hydroxyalkyl, aryl, aralkyl,cycloalkyl, heterocyclyl, ether, thioether, halogen, —N(R)₂,polyethylene polyamine, nitro, keto, ester, or carbonamide, optionallyalkyl substituted with alkyl, substituted alkyl, hydroxyalkyl, aryl,aralkyl, cycloalkyl, heterocyclyl, ether, thioether, halogen, —N(R)₂,polyethylene polyamine, nitro, keto, or ester; R⁹, R¹⁰, and R¹¹ areindependently hydrogen, alkyl, alkenyl or alkoxy of 1 to 36 carbons,cycloalkyl of 6 to 32 carbons, alkylamino of 1 to 36 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenyl, hydroxyalkyl,hydroxycycloalkyl of 1 to 20 carbon atoms, methoxyalkyl of 1 to 20carbon atoms, aralkyl of 7 to 9 carbon atoms (wherein the aryl group ofthe aralkyl is further substituted by alkyl of 1 to 36 carbon atoms,ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitrogroups, keto groups, ester groups, or carbonamide groups) (wherein thealkyl group of the aralkyl is optionally substituted with alkyl,substituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,heterocyclics, ether, thioether, halogen, —N(R)₂, polyethylenepolyamines, nitro groups, keto groups or ester groups), wherein the R of—N(R)₂ is alkyl, alkylene, aryl, aralkyl, cycloalkyl or heterocyclicradical, optionally substituted with halogen, nitro, alkyl, alkoxy oramino, and, when m =1, R is hydrogen or a plurality of radicalsoptionally joined by hetero atoms O, N or S; m is 1 or 2; n is 2 or 3;R₂₁-R₂₉ are independently hydrogen, alkyl, cycloalkyl, aryl, aromatic,ogranometallic, a polymeric structure, or together can form acycloalkyl, aryl, or an aromatic structure; a is 1, 2, or 3; and b is 1,2, or
 3. 5. The catalyst composition of claim 1, wherein the carboxylateis a carboxylate of a carboxylic acid of the following formula:

wherein R₁₁ is hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₁₆,a 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or6-membered heterocyclic ring which is benzo-fused and is unsubstitutedor substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; or aradical of one of the following formulae:

R₁₂, R₁₃, R₁₄ and R₁₅ are independently hydrogen, hydroxyl, C₁-C₁₈alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur; C₁-C₂₅alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substituted byC₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted or substitutedby C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkyl which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or are —COR₆, with the proviso that, if one of the radicals R₁₂, R₁₃,R₁₄ and R₁₅ is hydroxyl, the other radical attached to the same carbonatom is other than hydroxyl; or else R₁₂ and R₁₃ or R₁₄ and R₁₅,together with the carbon atom to which they are attached, form anunsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ring;R₁₆ is hydroxyl, C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted byoxygen or sulfur,

R₃₇, R₃₈, R₃₉, R₄₀, and R₄₁ are independently hydrogen, hydroxyl,halogen, nitro, cyano, CF₃, —COR₆, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈ alkoxy, C₂-C₁₈alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈ alkylthio,C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; phenoxy or naphthoxy which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkoxy which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkoxy which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or R₃₈and R₃₉, R₃₉ and R₄₀, R₄₀ and R₄₁, or R₃₇ and R₄₁, together withthe carbon atoms to which they are attached, form an unsubstituted orC₁-C₄ alkyl-, halogen- or C₁-C₄ alkoxy-substituted benzo ring, with theproviso that at least one of the radicals R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ ishydrogen; R₄₂ is hydroxyl, halogen, nitro, cyano, CF₃, C₁-C₂₅ alkyl,C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl,C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxgyen or sulfur;C₁-C₁₈ alkylthio; or C₂-C₂₄ alkenyl; R₄₃ and R₄₄ are independentlyhydrogen, C₁-C₂₅ alkyl, C₁-C₁₈ alkoxy or —Y—(CH₂)_(s)COR₆; R₄₅ and R₄₆are independently hydrogen, C₁-C₂₅ alkyl, C₃-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl whichis unsubstituted or substituted by C₁-C₄ alkyl; phenyl or naphthyl whichis unsubstituted or substituted by C₁-C₄ alkyl; X₁₁ is a direct bond,oxygen, sulfur, C(O), C₁-C₁₈ alkylene, C₂-C₁₈ alkylene which isinterrupted by oxygen or sulfur; C₂-C₁₈ alkenylene, C₂-C₁₈ alkynylene,C₂-C₂₀ alkylidene, C₇-C₂₀ phenylalkylidene or C₅-C₈ cycloalkylene, withthe proviso that, if m and n are 0, X₁₁ is other than oxygen and sulfur;Y is oxygen or

R_(a) is hydrogen or C₁-C₈ alkyl; e and f are independently integersfrom 0 to 10; p is an integer from 0 to 4; and s is an integer from 1 to8.
 6. The catalyst composition of claim 2, wherein the metal of themetal amidine complex and the metal of the metal carboxylate areindependently zinc or bismuth.
 7. The catalyst composition of claim 3,wherein the amidine of the metal amidine complex is an amidine offormula II or IV.
 8. The catalyst composition of claim 7, wherein theamidine is 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.
 9. Thecatalyst composition of claim 1, wherein the carboxylate is octoate,neodecanoate, naphthenate, stearate, or oxalate.
 10. The catalystcomposition of claim 1, wherein the second compound is a zinccarboxylate.
 11. The catalyst composition of claim 1, wherein the secondcompound is a bismuth carboxylate.
 12. The catalyst composition of claim1, wherein the second compound is a carboxylic acid.
 13. The catalystcomposition of claim 1, wherein the metal amidine complex is of thechemical formula metal(amidine)₂(carboxylate)_(x), wherein x is theoxidation state of the metal.
 14. A catalyst composition comprising ametal amidine complex and a second compound, wherein the metal amidinecomplex comprises a carboxylate and wherein the second compound is ametal carboxylate or a carboxylic acid, wherein the carboxylate of themetal amidine complex and the carboxylate of the metal carboxylate arenot identical.
 15. The catalyst composition of claim 14, wherein themetal amidine complex is of the chemical formulaM(amidine)_(w)(carboxylate)₂, wherein w is an integer from 1 to
 4. 16.The catalyst composition of claim 14, wherein the metal of the metalamidine complex and the metal of the metal carboxylate are independentlyzinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth,cadmium, aluminum, zirconium, tin, hafnium, titanium, lanthanum,vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.17. The catalyst composition of claim 14, wherein the amidine of themetal amidine complex is an amidine of one of formulae I-VIII:

wherein R¹ is hydrogen, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl, an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms; R² and R³ are eachindependently hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, or C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl, or R² and R³ are joinedto one another by an N═C—N linkage to form a heterocyclic ring with oneor more hetero atoms or a fused bicyclic ring with one or moreheteroatoms; R⁴ is hydrogen, C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or ahydroxyl group which can be optionally etherified with a hydrocarbylgroup having up to 8 carbon atoms; R⁵, R⁶, R⁷, and R⁸ are independentlyhydrogen, alkyl, substituted alkyl, hydroxyalkyl, aryl, aralkyl,cycloalkyl, heterocyclyl, ether, thioether, halogen, —N(R)₂,polyethylene polyamine, nitro, keto, ester, or carbonamide, optionallyalkyl substituted with alkyl, substituted alkyl, hydroxyalkyl, aryl,aralkyl, cycloalkyl, heterocyclyl, ether, thioether, halogen, —N(R)₂,polyethylene polyamine, nitro, keto, or ester; R⁹, R¹⁰, and R¹¹ areindependently hydrogen, alkyl, alkenyl or alkoxy of 1 to 36 carbons,cycloalkyl of 6 to 32 carbons, alkylamino of 1 to 36 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenyl, hydroxyalkyl,hydroxycycloalkyl of 1 to 20 carbon atoms, methoxyalkyl of 1 to 20carbon atoms, aralkyl of 7 to 9 carbon atoms (wherein the aryl group ofthe aralkyl is further substituted by alkyl of 1 to 36 carbon atoms,ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitrogroups, keto groups, ester groups, or carbonamide groups) (wherein thealkyl group of the aralkyl is optionally substituted with alkyl,substituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,heterocyclics, ether, thioether, halogen, —N(R)₂, polyethylenepolyamines, nitro groups, keto groups or ester groups), wherein the R of—N(R)₂ is alkyl, alkylene, aryl, aralkyl, cycloalkyl or heterocyclicradical, optionally substituted with halogen, nitro, alkyl, alkoxy oramino, and, when m =1, R is hydrogen or a plurality of radicalsoptionally joined by hetero atoms O, N or S; m is 1 or 2; n is 2 or 3;R₂₁-R₂₉ are independently hydrogen, alkyl, cycloalkyl, aryl, aromatic,ogranometallic, a polymeric structure, or together can form acycloalkyl, aryl, or an aromatic structure; a is 1, 2, or 3; and b is 1,2, or
 3. 18. The catalyst composition of claim 14, wherein thecarboxylate is a carboxylate of a carboxylic acid of the followingformula:

wherein R₁₁ is hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₁₆,a 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or6-membered heterocyclic ring which is benzo-fused and is unsubstitutedor substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; or aradical of one of the following formulae:

R₁₂, R₁₃, R₁₄ and R₁₅ are independently hydrogen, hydroxyl, C₁-C₁₈alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur; C₁-C₂₅alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substituted byC₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted or substitutedby C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkyl which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or are —COR₆, with the proviso that, if one of the radicals R₁₂, R₁₃,R₁₄ and R₁₅ is hydroxyl, the other radical attached to the same carbonatom is other than hydroxyl; or else R₁₂ and R₁₃ or R₁₄ and R₁₅,together with the carbon atom to which they are attached, form anunsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ring;R₁₆ is hydroxyl, C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted byoxygen or sulfur,

R₃₇, R₃₈, R₃₉, R₄₀, and R₄₁ are independently hydrogen, hydroxyl,halogen, nitro, cyano, CF₃, —COR₆, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈ alkoxy, C₂-C₁₈alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈ alkylthio,C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; phenoxy or naphthoxy which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkoxy which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkoxy which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or R₃₈ and R₃₉, R₃₉ and R₄₀, R₄₀ and R₄₁ or R₃₇ and R₄₁, together withthe carbon atoms to which they are attached, form an unsubstituted orC₁-C₄ alkyl-, halogen- or C₁-C₄ alkoxy-substituted benzo ring, with theproviso that at least one of the radicals R₃₇, R₃₈, R₃₉, R₄₀, and R₄₁ ishydrogen; R₄₂ is hydroxyl, halogen, nitro, cyano, CF₃, C₁-C₂₅ alkyl,C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl,C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxgyen or sulfur;C₁-C₁₈ alkylthio; or C₂-C₂₄ alkenyl; R₄₃ and R₄₄ are independentlyhydrogen, C₁-C₂₅ alkyl, C₁-C₁₈ alkoxy or —Y—(CH₂)_(s)COR₆; R₄₅ and R₄₆are independently hydrogen, C₁-C₂₅ alkyl, C₃-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl whichis unsubstituted or substituted by C₁-C₄ alkyl; phenyl or naphthyl whichis unsubstituted or substituted by C₁-C₄ alkyl; X₁₁ is a direct bond,oxygen, sulfur, C(O), C₁-C₁₈ alkylene, C₂-C₁₈ alkylene which isinterrupted by oxygen or sulfur; C₂-C₁₈ alkenylene, C₂-C₁₈ alkynylene,C₂-C₂₀ alkylidene, C₇-C₂₀ phenylalkylidene or C₅-C₈ cycloalkylene, withthe proviso that, if m and n are 0, X₁₁ is other than oxygen and sulfur;Y is oxygen or

R_(a) is hydrogen or C₁-C₈ alkyl; e and f are independently integersfrom 0 to 10; p is an integer from 0 to 4; and s is an integer from 1 to8.
 19. The catalyst composition of claim 16, wherein the metal of themetal amidine complex and the metal of the metal carboxylate areindependently zinc or bismuth.
 20. The catalyst composition of claim 17,wherein the amidine of the metal amidine complex is an amidine offormula I or IV.
 21. The catalyst composition of claim 14, wherein theamidine is 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.
 22. Thecatalyst composition of claim 14, wherein the carboxylate is octoate,neodecanoate, naphthenate, stearate, or oxalate.
 23. The catalystcomposition of claim 14, wherein the second compound is a zinccarboxylate.
 24. The catalyst composition of claim 14, wherein thesecond compound is a bismuth carboxylate.
 25. The catalyst compositionof claim 14, wherein the second compound is a carboxylic acid.
 26. Thecatalyst composition of claim 14, wherein the metal amidine complex isof the chemical formula metal(amidine)₂(carboxylate)_(x), wherein x isthe oxidation state of the metal.
 27. A catalyst composition comprisinga metal amidine complex and a second compound, wherein the secondcompound is a metal carboxylate or a carboxylic acid, wherein thecomposition is substantially free of free amidine and wherein the metalis not tin.
 28. The catalyst composition of claim 27, wherein the metalamidine complex is of the chemical formula M(amidine)_(w)(carboxylate)₂,wherein w is an integer from 1 to
 4. 29. The catalyst composition ofclaim 27, wherein the metal of the metal amidine complex and the metalof the metal carboxylate are independently zinc, lithium, sodium,magnesium, barium, potassium, calcium, bismuth, cadmium, aluminum,zirconium, hafnium, titanium, lanthanum, vanadium, niobium, tantalum,tellurium, molybdenum, tungsten, or cesium.
 30. The catalyst compositionof claim 27, wherein the amidine of the metal amidine complex is anamidine of one of formulae I-VIII:

wherein R¹ is hydrogen, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl, an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms; R² and R³ are eachindependently hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl; C₁₃-C₂₆polycycloalkyl, or C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl, or R² and R³ are joinedto one another by an N═C—N linkage to form a heterocyclic ring with oneor more hetero atoms or a fused bicyclic ring with one or moreheteroatoms; R⁴is hydrogen, C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or ahydroxyl group which can be optionally etherified with a hydrocarbylgroup having up to 8 carbon atoms; R⁵, R⁶, R⁷, and R⁸ are independentlyhydrogen, alkyl, substituted alkyl, hydroxyalkyl, aryl, aralkyl,cycloalkyl, heterocyclyl, ether, thioether, halogen, —N(R)₂,polyethylene polyamine, nitro, keto, ester, or carbonamide, optionallyalkyl substituted with alkyl, substituted alkyl, hydroxyalkyl, aryl,aralkyl, cycloalkyl, heterocyclyl, ether, thioether, halogen, —N(R)₂,polyethylene polyamine, nitro, keto, or ester; R⁹, R¹⁰, and R¹¹ areindependently hydrogen, alkyl, alkenyl or alkoxy of 1 to 36 carbons,cycloalkyl of 6 to 32 carbons, alkylamino of 1 to 36 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenyl, hydroxyalkyl,hydroxycycloalkyl of 1 to 20 carbon atoms, methoxyalkyl of 1 to 20carbon atoms, aralkyl of 7 to 9 carbon atoms (wherein the aryl group ofthe aralkyl is further substituted by alkyl of 1 to 36 carbon atoms,ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitrogroups, keto groups, ester groups, or carbonamide groups) (wherein thealkyl group of the aralkyl is optionally substituted with alkyl,substituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,heterocyclics, ether, thioether, halogen, —N(R)₂, polyethylenepolyamines, nitro groups, keto groups or ester groups), wherein the R of—N(R)₂ is alkyl, alkylene, aryl, aralkyl, cycloalkyl or heterocyclicradical, optionally substituted with halogen, nitro, alkyl, alkoxy oramino, and, when m =1, R is hydrogen or a plurality of radicalsoptionally joined by hetero atoms O, N or S; m is 1 or 2; n is 2 or 3;R₂₁-R₂₉ are independently hydrogen, alkyl, cycloalkyl, aryl, aromatic,ogranometallic, a polymeric structure, or together can form acycloalkyl, aryl, or an aromatic structure; a is 1, 2, or 3; and b is 1,2, or
 3. 31. The catalyst composition of claim 27, wherein thecarboxylate is a carboxylate of a carboxylic acid of the followingformula:

wherein R₁₁ is hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₁₆,a 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or6-membered heterocyclic ring which is benzo-fused and is unsubstitutedor substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; or aradical of one of the following formulae:

R₁₂, R₁₃, R₁₄, and R₁₅ are independently hydrogen, hydroxyl, C₁-C₁₈alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur; C₁-C₂₅alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substituted byC₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted or substitutedby C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkyl which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or are —COR₆, with the proviso that, if one of the radicals R₁₂, R₁₃,R₁₄, and R₁₅ is hydroxyl, the other radical attached to the same carbonatom is other than hydroxyl; or else R₁₂ and R₁₃ or R₁₄ and R₁₅,together with the carbon atom to which they are attached, form anunsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ring;R₁₆ is hydroxyl, C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted byoxygen or sulfur,

R₃₇, R₃₈, R₃₉, R₄₀, and R₄₁ are independently hydrogen, hydroxyl,halogen, nitro, cyano, CF₃, —COR₆, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈ alkoxy, C₂-C₁₈alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈ alkylthio,C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; phenoxy or naphthoxy which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkoxy which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkoxy which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or R₃₈ and R₃₉, R₃₉ and R₄₀, R₄₀ and R₄₁, or R₃₇ and R₄₁, together withthe carbon atoms to which they are attached, form an unsubstituted orC₁-C₄ alkyl-, halogen- or C₁-C₄ alkoxy-substituted benzo ring, with theproviso that at least one of the radicals R₃₇, R₃₈, R₃₉, R₄₀, and R₄₁ ishydrogen; R₄₂ is hydroxyl, halogen, nitro, cyano, CF₃, C₁-C₂₅ alkyl,C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl,C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxgyen or sulfur;C₁-C₁₈ alkylthio; or C₂-C₂₄ alkenyl; R₄₃ and R₄₄ are independentlyhydrogen, C₁-C₂₅ alkyl, C₁-C₁₈ alkoxy or —Y—(CH₂)_(s) COR₆; R₄₅ and R₄₆are independently hydrogen, C₁-C₂₅ alkyl, C₃-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl whichis unsubstituted or substituted by C₁-C₄ alkyl; phenyl or naphthyl whichis unsubstituted or substituted by C₁-C₄ alkyl; X₁₁ is a direct bond,oxygen, sulfur, C(O), C₁-C₁₈ alkylene, C₂-C₁₈ alkylene which isinterrupted by oxygen or sulfur; C₂-C₁₈ alkenylene, C₂-C₁₈ alkynylene,C₂-C₂₀ alkylidene, C₇-C₂₀ phenylalkylidene or C₅-C₈ cycloalkylene, withthe proviso that, if m and n are 0, X₁₁ is other than oxygen and sulfur;Y is oxygen or

R_(a) is hydrogen or C₁-C₈ alkyl; e and f are independently integersfrom 0 to 10; p is an integer from 0 to 4; and s is an integer from 1 to8.
 32. The catalyst composition of claim 29, wherein the metal of themetal amidine complex and the metal of the metal carboxylate areindependently zinc or bismuth.
 33. The catalyst composition of claim 30,wherein the amidine of the metal amidine complex is an amidine offormula I or IV.
 34. The catalyst composition of claim 33, wherein theamidine is 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.
 35. Thecatalyst composition of claim 27, wherein the carboxylate is octoate,neodecanoate, naphthenate, stearate, or oxalate.
 36. The catalystcomposition of claim 27, wherein the second compound is a zinccarboxylate.
 37. The catalyst composition of claim 27, wherein thesecond compound is a bismuth carboxylate.
 38. The catalyst compositionof claim 27, wherein the second compound is a carboxylic acid.
 39. Thecatalyst composition of claim 27, wherein the metal amidine complex isof the chemical formula metal(amidine)₂(carboxylate)_(x), wherein x isthe oxidation state of the metal.
 40. A coating composition comprising acatalyst composition of claim
 27. 41. The coating composition of claim40, further comprising a binder having uretdione groups and optionallyisocyanate groups.
 42. The coating composition of claim 40, furthercomprising an acid scavenger.
 43. The coating composition of claim 42,further comprising (a) an epoxy compound; and (b) a carboxyl, ananhydride, a dicyandiamide (DICY), or a phenolic compound.
 44. Thecoating composition of claim 40, further comprising (a) a bisphenol Aepoxy/amino resin with an equivalent weight of from about 200 to about2000; and (b) an aromatic or aliphatic isocyanate with a removableblocking group.
 45. The coating composition of claim 40, furthercomprising an organic film-forming binder.
 46. The coating compositionof claim 40, further comprising (a) a cationic resin; and (b) a cappedpolyisocyanate.
 47. The coating composition of claim 46, wherein thecationic resin is an epoxy-amine reaction product of a bisphenol A epoxyresin with an epoxy equivalent weight of between 200 and 2000 and aprimary amine, a secondary amine, or a tertiary amine.
 48. The coatingcomposition of claim 40, further comprising (a) a polyol; and (b) apolyisocyanate.
 49. The coating composition of claim 40, furthercomprising (a) a binder; and (b) a hardener.
 50. The coating compositionof claim 49, wherein the hardener is an aromatic or aliphatic isocyanateand wherein the isocyanate contains a removable blocking group.